JP4891042B2 - toner - Google Patents

Description

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

  As a general electrophotographic image forming method, for example, a photoconductive substance is used, an electric latent image is formed on an electrostatic latent image carrier by various means, and the latent image is formed by a developing device. Visualization by developing to a toner image, and then transferring the toner image to a transfer material such as paper as necessary, and then fixing by heating, pressure, heating and pressurization or solvent vapor to obtain a toner image It has been known.

  In recent years, the technical direction of image forming devices requires high definition, high quality, and high image quality, as well as higher speed and long-term reliability. As described above, the hardware configuration is configured with simple elements in various respects.

  That is, in order to provide excellent hardware, it is very important to further improve the performance of the toner. For example, one of the most important performances required for the toner is fixing performance.

  In particular, there is a strong demand for excellent low-temperature fixing performance of toners in order to cope with recent energy savings and higher speeds. However, pursuing low-temperature fixing properties deteriorates offset resistance and blocking resistance at high temperatures. Problems arise. In view of this, various toners have been proposed in order to satisfy both the low-temperature fixability and the resistance to offset and blocking at high temperatures.

  Patent Document 1 discloses a modified polyethylene wax using a styrene monomer and / or an unsaturated carboxylic acid derivative monomer.

  Further, Patent Document 2 discloses a developer composition using a polyester resin as a binder resin and a grafted polyolefin wax as a wax.

  Further, Patent Document 3 proposes coexistence of fixability and hot offset resistance by low molecular weight polypropylene and modified polyethylene.

  All of these have improved fixing performance to some extent, but are insufficient to satisfy both the low-temperature fixing ability that can cope with the recent increase in speed, the hot offset resistance and the blocking resistance.

  Patent Documents 4 to 6 propose that the toner contains two types of wax components in order to obtain a toner having excellent low-temperature fixability and offset resistance.

  Patent Documents 13 to 15 propose that two types of toner contain waxes having different melting points.

  Further, Patent Documents 7 to 10 propose a toner that uses a polyester resin or a hybrid resin as a binder resin to expand the fixing region, and uses a modified wax to improve wax dispersibility. Yes.

  Patent Documents 11 and 12 disclose waxes having a specified hydroxyl value in order to achieve both good fixability and durable developability.

  However, even if any of these release agents is used, the range of low-temperature fixability and high-temperature offset resistance will surely expand, but toner deterioration will occur due to high durability, and it will be stable over a long period of time. It was totally insufficient for practical use.

  In particular, when applied to a high-speed development system using a high-capacity cartridge with a high process speed, the high-speed fixing property is often insufficient. When the toner is durable for a long period of time, free wax and toner with poor wax dispersion tend to accumulate on the developing sleeve, and image streaks and image density decrease due to fusion on the developing sleeve.

  In recent years, toner has been spheroidized for the purpose of improving image quality and reducing consumption. However, when the regulation of the toner coat layer on the developing sleeve has been strengthened in response to the spheroidization, the above-mentioned problems have occurred. There was a case that became apparent.

  Further, in a large-capacity cartridge corresponding to a high-speed developing system, the toner is easily stressed due to the weight of the toner. Therefore, depending on the transportation form from shipment to delivery to the user and the storage conditions such as heat cycle, wax of the prior art was likely to ooze out on the toner surface or to cause packing in the cartridge. . In some cases, when the user tries to output, the density is low or it is covered.

  That is, development of a toner that matches the recent high-speed development system based on energy saving and a large capacity cartridge has been desired.

Japanese Patent No. 2520892 Japanese Patent No. 2698574 JP-A-7-281478 JP-A-8-278657 JP-A-8-334919 JP-A-8-334920 JP 2003-84483 A JP-A-2005-84580 JP 2003-50476 A JP 2003-98726 A JP 2001-343781 A JP 2003-302784 A JP 2000-75556 A JP 2000-131889 A JP 2001-194830 A

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

  That is, the object of the present invention is to have excellent high-speed fixability, high durability, and excellent developability even when applied to a high-speed development system using a large-capacity cartridge with a high process speed. It is to provide a toner that can be used.

  In addition, the object of the present invention is to prevent the wax from oozing out on the toner surface even when stored in harsh conditions in a large-capacity cartridge and to suppress packing in the cartridge, so that the user can output an initial image. Another object of the present invention is to provide a toner capable of outputting an excellent image.

As a result of intensive studies, the present inventors have found that in a toner containing at least a binder resin having a polyester unit and wax A and wax B,
The wax A has at least one polar group selected from a carboxyl group, a hydroxyl group, and an ester group,
It has been found that the object of the present invention can be achieved with a toner characterized in that the wax B is a modified hydrocarbon wax grafted with a styrene-based or styrene-acrylic polymer.

  According to the toner of the present invention, the process speed is high, and even when applied to a high-speed development system using a large-capacity cartridge, it has excellent high-speed fixing properties and maintains excellent developability with high durability. It is possible to provide a toner that can be used. Further, it is possible to provide a toner that can output an excellent image when a user outputs an initial image even when stored in a severe condition in a large-capacity cartridge.

  In a toner containing a binder resin having at least a polyester unit and wax A and wax B, the wax A has at least one polar group selected from a carboxyl group, a hydroxyl group, and an ester group, According to the toner in which the wax B is a modified hydrocarbon wax grafted with a styrene or styrene acrylic polymer, the object of the present invention can be achieved.

  That is, it contains a binder resin having a polyester unit, and the wax A has one or more polar groups among a carboxyl group, a hydroxyl group, and an ester group. Wax A is finely dispersed in the resin and partly compatible. As a result, the low-temperature fixing performance can be remarkably improved as compared with the case where the wax A does not have a polar group.

  Furthermore, by using a modified hydrocarbon wax grafted with a styrene-based or styrene-acrylic polymer as the wax B, an appropriate dispersion diameter is maintained without being too compatible with the binder resin having a polyester unit. To do. For this reason, it is possible to maintain good hot offset resistance when the binder resin having the polyester unit is fixed.

  That is, by simultaneously using the wax A and the wax B for the binder resin having a polyester unit, both excellent low-temperature fixability and hot offset resistance can be achieved. The inventors of the present invention have found that the simultaneous use of wax A and wax B greatly expands the fixable range due to the synergistic effect of both, rather than a single contribution to each fixability.

  Furthermore, it has been found that by using both waxes in combination, even if the toner is stored under severe conditions in, for example, a large capacity cartridge, the exudation of wax can be suppressed to the maximum.

  About the synergistic effect of these two waxes, the reason is not clear, but probably the following phenomenon.

  That is, it is considered that both waxes play a role of dispersing aids and prevent excessive compatibility. For the binder resin having a polyester unit, the wax A exists so as to surround the wax B that should have an appropriate dispersion diameter, and acts as a dispersion aid to uniformly distribute the wax B in the resin. Can exist. On the contrary, the wax A is partially compatible with the resin in order to realize excellent high-speed fixability. However, if it is excessively compatible, the fixability may be deteriorated or the environment may be harsh. Preservability at is easy to deteriorate. However, it is considered that the presence of the wax B at the same time prevents the wax A from being excessively compatible by the interaction with the wax B and can achieve an appropriate compatible state.

  In a further preferred embodiment of the present invention, the binder resin contains at least a resin component having a polyester unit and a resin component having a vinyl copolymer unit.

  By further containing a resin having a vinyl copolymer unit, the resin having a vinyl copolymer unit is dispersed in the binder resin having a polyester unit that contributes to low-temperature fixability, and hot-resistant around it. Since the wax B that greatly contributes to the offset property is finely dispersed moderately, excellent hot offset resistance can be exhibited while maintaining good low-temperature fixability.

  In particular, when the ratio of the resin component having a vinyl copolymer unit in the binder resin is Sr (mass%), Sr is preferably 5.0 to 50.0, and more preferably 5.0. To 40.0. When Sr is less than 5.0, the fine dispersibility of the wax B becomes insufficient, and the durability developability and the hot offset resistance tend to be inferior. On the other hand, when Sr exceeds 50.0, the low-temperature fixing performance of the binder resin itself tends to deteriorate, and it becomes difficult to satisfy the high-speed fixing performance required for a high-speed machine.

In order to maximize the hot offset resistance due to the wax B, when the ratio of the styrene-based or styrene-acrylic polymer in the wax B is Sw (mass%), Sw and the Sr can simultaneously satisfy the following two formulas: It is more preferable to satisfy.
Sw ≦ −2Sr + 100.0
5.0 ≦ Sw ≦ 70.0

  By simultaneously satisfying the above two formulas, the wax B can be appropriately finely dispersed in the binder resin, and can exhibit excellent hot offset resistance while exhibiting good low-temperature fixability. .

  In addition, by satisfying the above two formulas at the same time, the present inventors can exude wax from the toner surface even when the toner is placed in a harsh environment under stressful conditions such as a large capacity cartridge. I found it easy to be suppressed.

  The reason for this is not clear, but it is probably due to the fact that the roles of both waxes as mutual dispersion aids are maximized as described above.

  More preferably, the DSC melting peak temperature of the wax A is lower than the DSC melting peak temperature of the wax B. The DSC melting peak temperature of the wax A is more preferably 10 ° C. or more lower than the DSC melting peak temperature of the wax B, and more preferably 20 ° C. or more.

  In order to achieve both excellent low-temperature fixing performance and high-temperature offset-resistant performance, it is preferable that there is a difference in DSC melting peak temperature between the two types of waxes. In particular, a binder resin having a polyester unit that greatly contributes to low-temperature fixing properties. It is preferable that the DSC melting peak temperature of the wax A that is finely dispersed and compatible with the wax B is low, and the wax B has a DSC melting peak temperature higher than that of the wax A.

  In the present invention, it is important that the wax A has at least one polar group selected from a carboxyl group, a hydroxyl group, and an ester group. In particular, a polar wax having a hydroxyl group is preferable from the viewpoint of chargeability of the toner.

  The wax A used in the present invention preferably contains a hydrocarbon molecular chain having the following structure.

  That is, it is essential to have at least a molecular chain having a secondary alcohol structure having a hydroxyl group on a secondary carbon, or a molecular chain having a primary alcohol structure having a hydroxyl group on a primary carbon, which can be represented by the following partial structural formulas A to E. And At the same time, it is essential to have a molecular chain having a carboxyl group in primary or secondary carbon, which can be represented by the following partial structural formulas C to D. The following partial structural formulas A to E and C to D may each have both in one hydrocarbon chain. Furthermore, you may have the molecular chain which has the structure of the ester which can represent with the following partial structural formula B and has an ester bond. More preferably, it is a hydrocarbon chain having a molecular chain having an alcohol structure represented by the following partial structural formulas A to E, C to D, and B, a carboxyl group, and an ester bond.

  Moreover, you may have the structure of arbitrary following partial structural formula A, B, C, D, and E in one hydrocarbon chain.

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

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

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

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

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

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

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

  The acid value (WAv) of the wax A used in the present invention is preferably 1 to 30 mgKOH / g or less (preferably 1 to 15 mgKOH / g or less, more preferably 2 to 10 mgKOH / g or less).

  Since the wax A has an acid group, the interfacial adhesive force with other components constituting the toner particles is likely to be increased, the effect of plasticizing the toner is increased, and the fixing property of the toner is easily improved. When the acid value of the wax A is less than 1 mgKOH / g, the interfacial adhesive force with other components constituting the toner particles tends to be small, the wax is likely to be liberated, and the effect of the wax may not be sufficiently obtained. . On the other hand, when the acid value of the wax A is larger than 30 mgKOH / g, the interfacial adhesive force is excessively increased, the toner plasticization is greatly advanced, and sufficient releasability may not be maintained.

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

  By having an appropriate hydroxyl group in the molecule of the wax A, the wax A can be dispersed in the binder resin in the form of fine particles, so that an appropriate plastic effect is obtained and the fixability is improved. When the hydroxyl value of the wax A is less than 5 mgKOH / g, the toner A may not be sufficiently finely dispersed, and the toner fixability may be lowered. On the other hand, when the hydroxyl value of the wax is greater than 100 mgKOH / g, the plasticizing effect of the hydrocarbon wax becomes too great, and the blocking resistance of the toner may be lowered.

The ester value (WEv) of the wax A used in the present invention is 1 to 50 mgKOH / g (preferably 1 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g, and particularly preferably 1 to 15 mgKOH / g. g). Furthermore, it is preferable that the relationship between the hydroxyl value and the ester value satisfies the following formula (I).
WOHv> WEv (I)

  If the ester value of the wax A is less than 1 mgKOH / g, the effect of the wax A on the toner fixability may be lowered. On the other hand, if the ester value of wax A is greater than 50 mgKOH / g, the affinity of wax A to the binder resin becomes too high, and the binder resin is likely to deteriorate, and the developability of the toner is poor in long-term use. May be.

  When the ester value of the wax A is higher than the hydroxyl value, the affinity between the wax A and the binder resin is increased, and the wax is less likely to ooze onto the surface of the toner particles, affecting the low-temperature fixability and offset resistance of the toner. It may become like this.

  In addition, the ester group in the wax A has a high affinity with the binder resin component, and the hydroxyl group has a high affinity with the fixing sheet such as paper, so that the toner is discharged from the fixing member. As a result, the releasability between the toner and the fixing member and the discharge property to the fixing sheet are improved, and excellent low-temperature fixing property and offset resistance can be exhibited.

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

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

  When the number average molecular weight of the wax A is less than 100, the wax A is excessively susceptible to thermal influence, and the blocking resistance and developability may be deteriorated. If the number average molecular weight of the hydrocarbon wax is greater than 3,000, heat from the outside cannot be used effectively, and excellent fixability may not be obtained. The number average molecular weight of the hydrocarbon wax can be measured by the method described later. In addition, the number average molecular weight of the hydrocarbon wax is, for example, (adjustment of the number average molecular weight associated with the type of aliphatic hydrocarbon wax used as a raw material for the hydrocarbon wax, or a production method such as synthesis, thermal decomposition, or petroleum extraction). It is possible to adjust. Further, as a method for adjusting the acid value, the hydroxyl value, and the ester value, a boric acid ester of a hydrocarbon wax is generated from the aliphatic hydrocarbon wax described above, and the boric acid ester of the hydrocarbon wax is hydrolyzed. In the process, the number average molecular weight also changes due to thermal decomposition. Therefore, the number average molecular weight can be adjusted by combining different types of hydrocarbon waxes.

  The DSC melting peak temperature of the wax A is preferably 55 ° C to 90 ° C, more preferably 60 ° C to 85 ° C. More preferably, it is 65 ° C to 85 ° C. When the temperature is lower than 55 ° C., the storage stability of the toner tends to be lowered, and when the temperature is higher than 90 ° C., it is difficult to achieve high-speed fixing property of the toner.

  The DSC melting peak temperature of the wax can be measured by the method described later. Further, the DSC melting peak temperature of the wax A can be adjusted by, for example, reforming by the type of hydrocarbon wax or alcohol conversion.

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

  If the penetration of the hydrocarbon wax at 25 ° C. is less than 5, the compatibility with the binder resin is deteriorated, the dispersion of the wax in the toner particles is deteriorated, the chargeability is uneven, and the developability is improved. make worse. On the other hand, when the ratio is larger than 15, the storage stability (blocking resistance) of the toner at a high temperature may be deteriorated. In the present invention, the penetration of the hydrocarbon wax is determined according to JIS K-2235-5.4.

  In the present invention, the following ester wax may be used as the wax A.

  The following compounds are mentioned as a preferable ester compound which comprises ester wax. The ester wax suitably used in the present invention preferably has a weight average molecular weight (Mw) of 350 to 1500 from the viewpoint of improving low-temperature fixability and OHP transmittance. When Mw is less than 350, the fixability on the low temperature side does not work effectively, and when it exceeds 1500, the OHP transmittance tends to deteriorate.

（式中、ａ及びｂは０乃至４の整数であり、ａ＋ｂは４である。Ｒ₁及びＲ₂は炭素数が１乃至４０の有機基である。ｍ及びｎは０乃至４０の整数であり、ｍとｎは同時に０になることはない。）

(In the formula, a and b are integers of 0 to 4, a + b is 4. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. M and n are integers of 0 to 40. Yes, m and n are not 0 at the same time.)

（式中、ａ及びｂは０乃至３の整数であり、ａ＋ｂは１乃至３である。Ｒ₁及びＲ₂は炭素数が１乃至４０の有機基である。Ｒ₃は水素原子または炭素数が１以上の有機基である。ｋは１乃至３の整数であり、ａ＋ｂ＋ｋ＝４である。ｍ及びｎは０乃至４０の整数であり、ｍとｎが同時に０になることはない。）

(In the formula, a and b are integers of 0 to 3, a + b is 1 to 3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or a carbon number. Is an organic group of 1 or more, k is an integer of 1 to 3, and a + b + k = 4, m and n are integers of 0 to 40, and m and n are not 0 at the same time.)

（式中、Ｒ₁及びＲ₃は炭素数１乃至４０の有機基であり、Ｒ₁とＲ₃は同じものであっても異なっていても良い。Ｒ₂は炭素数１乃至４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ is an organic group having 1 to 40 carbon atoms. Is shown.)

（式中、Ｒ₁及びＲ₃は炭素数１乃至４０の有機基であり、Ｒ₁とＲ₃は同じものであってもなくてもよい。Ｒ₂は炭素数１乃至４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same. R ₂ represents an organic group having 1 to 40 carbon atoms. Show.)

（式中、ａは０乃至４の整数であり、ｂは１乃至４の整数であり、ａ＋ｂは４である。Ｒ₁は炭素数１乃至４０の有機基である。ｍ及びｎは０乃至４０の整数であり、ｍとｎが同時に０になることはない）

(Wherein, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. M and n are 0 to 4. (It is an integer of 40, and m and n cannot be 0 at the same time.)

  In the present invention, the following acid-modified wax may be used as the wax A.

  The acid monomer used for modification is preferably one containing at least one of a carboxyl group, a carboxylic acid anhydride group, and a carboxylate group, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, and crotonic acid. Acrylic acid and its α- or β-alkyl derivatives, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and monoester derivatives or anhydrides thereof, and these acid monomers can be used alone or in combination. Can be used.

  Among these, a wax modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride is preferable.

  In the present invention, it is important that the wax B is a modified hydrocarbon wax grafted with a styrene or styrene acrylic polymer.

  The original hydrocarbon wax before grafting the styrene-based or styrene-acrylic polymer may have an acid group or a hydroxyl group as in the case of the wax A, but in order to impart excellent releasability to the toner. It is preferable to use a nonpolar wax.

  That is, as the original hydrocarbon wax before grafting the styrene-based or styrene-acrylic polymer, natural paraffin wax, synthetic paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. are preferable, among which Fischer-Tropsch wax is preferred. Is particularly preferred. When the original hydrocarbon wax is Fischer-Tropsch wax, it is easy to achieve both high-speed fixing properties and high durability as compared with the case of polyolefin waxes such as polyethylene and polypropylene.

  The reason for this is not clear, but perhaps the characteristics of Fischer-Tropsch wax, which are almost completely straight chain molecular structure, have been maintained to some extent even after graft modification, resulting in high fast fixability and high stability. This is thought to be effective for durability.

  Examples of the styrene monomer include styrene, α-methyl styrene, vinyl toluene, isopropenyl toluene, p-methyl styrene, p-methoxy styrene, m-methyl styrene and the like.

  A modified hydrocarbon wax can be obtained using the above-described raw material wax and a styrene monomer in accordance with ordinary methods and conditions. Specifically, for example, a method using radiation or a method using a radical catalyst can be used, but a method using a radical catalyst is preferable.

  As radical catalysts, organic peroxides, organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl -2,5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octate, ter - butyl perpivalate, cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate; other azo compounds such as azobisisobutyronitrile, and the like dimethyl azoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert- Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The modified hydrocarbon wax used in the present invention includes a modified hydrocarbon wax grafted with a styrene-based or styrene-acrylic polymer, but preferably includes an unmodified hydrocarbon wax at the same time. . From the viewpoint of fixing properties, it is preferable that an unmodified hydrocarbon wax is present. However, the content of the modified hydrocarbon wax grafted with a styrene-based or styrene-acrylic polymer is M1 (mass%), and the unmodified carbonized wax is present. When the content of the hydrogen-based wax is M2 (mass%), the following formula 0.05 ≦ M2 / (M1 + M2) ≦ 0.90
It is preferable that More preferably, 0.15 ≦ M2 / (M1 + M2) ≦ 0.80
It is.

  If M2 / (M1 + M2) is greater than 0.90, the dispersion of the wax in the toner tends to be poor, which tends to be disadvantageous in terms of developability and durability. When M2 / (M1 + M2) is smaller than 0.05, the wax is difficult to work effectively at the time of fixing, and the fixing temperature width tends to be small.

  The modified hydrocarbon wax used in the present invention contains a polymer of a styrene monomer in addition to a modified hydrocarbon wax and an unmodified hydrocarbon wax grafted with a styrene or styrene acrylic polymer. However, this quantity ratio is not limited at all.

  The composition ratio of the unmodified hydrocarbon wax in the modified hydrocarbon wax was determined and classified as follows.

  GPC measurement of the hydrocarbon wax before modification and the modified hydrocarbon wax under the same conditions, the amount reduced from the GPC peak area of the hydrocarbon wax before modification is the styrene modified hydrocarbon wax, and the rest is the unmodified hydrocarbon The amount of the system wax was used.

  The modified hydrocarbon wax used in the present invention is preferably charged in an amount of 5 to 200 parts by mass of a styrene monomer with respect to 100 parts by mass of the hydrocarbon wax. When the styrene monomer is less than 5 parts by mass, it is difficult to obtain the effect as the modified wax described above. If the styrene monomer exceeds 200 parts by mass, it will be difficult to work effectively as a wax at the time of fixing, and the fixability tends to be disadvantageous.

  The DSC melting peak temperature of wax B is preferably 75 ° C to 130 ° C, more preferably 80 ° C to 120 ° C. More preferably, it is 85 to 110 ° C. When the temperature is lower than 75 ° C., the hot offset resistance of the toner tends to decrease, and when the temperature is higher than 130 ° C., it becomes difficult to achieve high-speed fixing property of the toner.

  In the present invention, the acid value, hydroxyl value, and ester value of the hydrocarbon wax (a) are determined by the following methods. The basic operation conforms to J1S K 0070.

<Measurement of acid value>
・ Equipment and instrument Erlenmeyer flask (300 ml)
Burette (25ml)
Water bath or hot plate ・ Reagent 0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ potassium hydroxide ethanol solution (standardization: 25 ml of 0.1 kmol / m ³ hydrochloric acid is taken into an Erlenmeyer flask using all pipettes, phenolphthalein Add the solution, titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
Phenolphthalein solution Solvent (diethyl ether and ethanol (99.5) mixed at a volume ratio of 1: 1 or 2: 1. These were added with a few drops of the phenolphthalein solution as an indicator immediately before use, and were added in an amount of 0.0. Neutralize with 1 kmol / m3 potassium hydroxide ethanol solution.)
Measurement method (a) Hydrocarbon wax (a) 1 to 20 g is precisely weighed into an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the hydrocarbon wax is completely dissolved in a water bath.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the light red color of the indicator lasts for 30 seconds.
・ Calculation A = 5.611 × B × f / S
However, A: Acid value (mgKOH / g)
B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass (g) of hydrocarbon wax (a)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

<Measurement of hydroxyl value>
・ Device and instrument graduated cylinder (100ml)
Full pipette (5ml)
Flat bottom flask (200ml)
Glycerin bath ・ Reagent Acetylation reagent (Place 25 g of acetic anhydride in a 100-mL volumetric flask, add pyridine to make a total volume of 100 mL, and shake well)
Phenolphthalein solution 0.5 kmol / m3 potassium hydroxide ethanol solution ・ Measuring method (a) 0.5 to 6.0 g of hydrocarbon-based wax is precisely weighed into a flat bottom flask, and 5 ml of acetylating reagent is added to the whole using a pipette. Add.
(B) Place a small funnel at the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
Calculation A = [{(BC) × 28.05 × f} / S] + D
Where A: hydroxyl value (mgKOH / g)
B: Amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test (ml)
C: Amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of hydrocarbon wax (g)
D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

<Measurement of ester value>
Calculated by the following formula.
(Ester value) = (Saponification value)-(Acid value)

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

  In the present invention, when the acid value, the hydroxyl value, and the ester value of the hydrocarbon wax (a) contained in the magnetic toner are measured, the hydrocarbon wax (a) is separated from the magnetic toner, and then the above-mentioned. You may measure according to a measuring method.

In the present invention, the DSC melting peak temperature of the hydrocarbon wax can be measured under the following conditions using a differential thermal analysis measuring device (DSC measuring device) and DSC2920 (manufactured by TA Instruments Japan).
Measuring method of DSC melting peak temperature of hydrocarbon wax Measured according to ASTM D3418.
Sample: 0.5 to 2 mg, preferably 1 mg
Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. to 180 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (180 ° C to 10 ° C, temperature drop rate 10 ° C / min)
Temperature rise II (10 ° C. to 180 ° C., temperature rise rate 10 ° C./min)

  The endothermic peak temperature measured at the temperature rise II in the temperature curve is defined as the DSC melting peak temperature.

  In the present invention, the molecular weight of the wax is measured by gel permeation chromatography (GPC) under the following conditions.

(GPC measurement conditions)
Apparatus: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% sample A molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  Samples are prepared as follows.

  Place the sample in o-dichlorobenzene and heat the sample bottle on a heater set at 150 ° C. to dissolve the sample. When the sample is melted, place it in a preheated filter unit and place it on the main unit. The sample passed through the filter unit is used as the GPC sample. The sample concentration is adjusted to 0.15% by mass.

  In the present invention, as the usable binder resin, various resin compounds conventionally known as binder resins can be used, but it is important to contain at least a binder resin having a polyester unit. is there.

  Conventionally known resins include, for example, vinyl resins, phenol resins, natural resin-modified phenol resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamides. Resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin, etc. can be used, and these resins can be used alone or in combination of two or more as the binder resin. it can.

  In the present invention, it is important to contain a binder resin having at least a polyester unit, and it is preferable to use a mixture of a polyester resin and a vinyl resin as the binder resin. Furthermore, it is particularly preferable that a hybrid resin component in which both of them partially react is included in order to achieve both chargeability, fixing property and storage stability, and to provide the binder resin with appropriate flexibility and mechanical strength. .

  The content of the polyester-based resin component in the present invention is a combination of the polyester-based resin component present in the polyester resin or the hybrid resin.

  The toner of the present invention preferably contains 3 to 50% by mass (preferably 5 to 40% by mass, more preferably 5 to 30% by mass) of a tetrahydrofuran-insoluble component (gel component) derived from the binder resin. Further, such a gel component preferably contains a hybrid resin that is a reaction product of a polyester resin component and a vinyl resin component. When the tetrahydrofuran insoluble content is less than 3% by mass, the high temperature resistant offset cannot be satisfied. When the tetrahydrofuran insoluble content is more than 50% by mass, it becomes difficult to uniformly disperse a material such as a colorant in the toner, the chargeability of the toner is deteriorated, fogging and a decrease in image density occur, and a wax is added. Dispersibility tends to be non-uniform and it is difficult to achieve the object of the present invention.

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

  In particular, the inclusion of the hybrid resin in the tetrahydrofuran-insoluble component (gel component) facilitates the presence of wax in the vicinity of the gel component in the toner. For this reason, the wax component is melted at the time of fixing, so that the gel component is easily softened, the sharp melt property of the toner is increased, and the fixing property is greatly improved. In addition, the inclusion of a hybrid resin in the gel component facilitates the incorporation of a colorant such as a magnetic substance that is not likely to enter the gel component into the gel component. Stability is improved, and developability and image quality are improved.

  In addition, the polyester resin component contained in the tetrahydrofuran-insoluble component is hydrolyzed, and the THF-soluble component of the vinyl resin component obtained as a residue has a molecular weight of 10,000 to 1,000,000 (preferably 20,000 to 500,000, more preferably 50,000 to 200,000). ), The polyester resin component is hybridized to the vinyl resin component having a large molecular weight. This makes it possible to obtain a gel structure having a large molecular weight and a large molecular weight between cross-linking points.

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

  The polyester resin component contained in the tetrahydrofuran insoluble content is hydrolyzed, and the main peak molecular weight of the THF soluble content of the vinyl resin component obtained as a residue is less than 10,000. Gets worse. Further, since the molecular weight between the crosslinking points is small, the gel component is not flexible, the gel component is easily cut by the shearing force at the time of kneading into toner, and the high temperature offset resistance is deteriorated. When the main peak molecular weight is larger than 1,000,000, it becomes difficult to uniformly disperse the gel component in the toner, and the developability deteriorates.

  The molecular weight distribution of the THF-soluble component of the vinyl resin component obtained by hydrolyzing the polyester resin component contained in the tetrahydrofuran-insoluble component as a 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 × 10 mm, manufactured by Toyo Filter Paper Co., Ltd.). Using 200 ml of tetrahydrofuran as a solvent, the tetrahydrofuran solubles are extracted for 16 hours. At this time, the extraction is performed at a reflux rate such that the extraction cycle of tetrahydrofuran is about once every 4 to 5 minutes. After completion of the extraction, the cylindrical filter paper is taken out, and the tetrahydrofuran-insoluble content of the toner on the cylindrical filter paper is collected.

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

(2) Separation of vinyl-based resin component by hydrolysis The tetrahydrofuran-insoluble matter derived from the resulting binder resin was dispersed in a 2 mol NaOH aqueous solution at a concentration of 1% by mass, and the polyester was obtained under the conditions of a pressure vessel, 150 ° C. and 24 hours. Hydrolyzes the resin component. The vinyl resin component is separated from this hydrolyzed solution by the following procedure.
i) The hydrolyzate was suction filtered using a membrane filter to separate the vinyl resin component as a residue. Thereby, the monomer component which is a decomposition product of the polyester resin component is removed in the filtrate.
ii) Since the vinyl resin component which is a residue is converted to a sodium salt by hydrolysis of the acrylic ester component contained in the vinyl resin component, the residue is added with dispersed hydrochloric acid in water to pH = 2 The COO-group generated by hydrolysis of the acrylic ester component contained in the vinyl resin component was protonated, and then filtered and separated with a membrane filter.

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

  The toner of the present invention has a main peak in the molecular weight range of 2000 to 30000 (preferably 3000 to 20000, more preferably 5000 to 10,000) in the GPC molecular weight distribution of the THF soluble content of the toner, and has a molecular weight of 40000 to It is preferable to contain 3 to 50 area% (preferably 3 to 30 area%, more preferably 5 to 20 area%) of components in the range of 1000000. In the molecular weight distribution of the THF soluble matter of the toner, it has a main peak in the low molecular weight region, contains a certain amount of components in the high molecular weight region, and further has a gel component as described above, thereby fixing at a high level. It is possible to provide stable developability (high durability) over a long period of use while maintaining the properties and high-temperature offset resistance.

  The hybrid resin component having a large molecular weight between cross-linking points easily incorporates a low molecular weight component having a peak molecular weight of 2000 to 30000 into the cross-linked structure, so that the gel component is easily melted by heat and the fixability is easily 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 high temperature offset property is easily improved. In addition, since the gel component is uniformly mixed in the toner, the pulverization property at the time of toner production is improved, and the ultrafine powder and coarse powder generated during the pulverization are greatly reduced. As a result, the factor that inhibits charging of the toner is reduced, and excellent development durability can be provided.

  If the main peak is less than 2,000, the storage stability and developability of the toner are likely to deteriorate, and if it is greater than 30,000, the fixability tends to deteriorate.

  When the component having a molecular weight in the range of 40000 to 1000000 is less than 3% by area, the uniform mixing property of the gel component tends to be lowered, and ultrafine powder and coarse powder are likely to be generated at the time of pulverization, and the development durability is likely to deteriorate. When the component having a molecular weight in the range of 40,000 to 1,000,000 is more than 30% by area, the toner viscosity becomes too high and the fixability tends to deteriorate.

  The binder resin used in the present invention can be used alone as a hybrid resin, for example, a mixture of a hybrid resin and a vinyl resin, a mixture of a hybrid resin and a polyester resin, or a polyester resin and a hybrid resin. And a mixture of vinyl resin and the like.

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

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

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

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

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

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

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

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

  In the production methods of (1) to (5) above, a polymer component having a plurality of different molecular weights and crosslinking degrees can be used as the vinyl resin component and / or the polyester resin component.

  The production method particularly preferably used in the present invention includes (3). Among them, an unsaturated polyester resin capable of reacting with a vinyl monomer is dissolved in the vinyl monomer, and a mixture of the polyester resin and the vinyl monomer is prepared. Those obtained by polymerization by a bulk polymerization method are preferred.

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

  In the bulk polymerization method, a binder resin can be obtained at low cost because a step such as evaporation of the solvent is not necessary as compared with the solution polymerization method. Compared with the suspension polymerization method, it does not contain impurities such as dispersants, so it has a great merit as a binder resin for toners. ,preferable.

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

  The unsaturated polyester resin component used in the hybrid resin obtained by the bulk polymerization method has a molecular weight distribution of 2000 to 30000 (preferably 3000 to 20000, more preferably 5000 to 10000) in the GPC molecular weight distribution of THF soluble matter. A low molecular weight unsaturated polyester resin component having a main peak is preferably used. Furthermore, the linear unsaturated polyester resin component which does not contain a gel component is especially preferable. If the main peak molecular weight is less than 2000, the developability tends to deteriorate, and if it exceeds 30000, the fixability tends to deteriorate.

  Further, the unsaturated polyester resin component used in the present invention has a number average molecular weight (Mn) of 2000 to 20000, preferably 3000 to 10,000. When the number average molecular weight (Mn) is less than 2000, a gel component is hardly generated in the hybrid resin, and high temperature offset resistance and development durability are likely to deteriorate. When the number average molecular weight (Mn) is larger than 20000, the solubility of the unsaturated polyester resin component in the vinyl monomer is lowered, and it becomes difficult to obtain a hybrid resin by bulk polymerization. The polyester resin component and the vinyl resin In addition to the separation of the components and the deterioration of the chargeability of the toner, it is difficult to make the circularity and the modification degree uniform in different particle size regions.

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

  By bulk polymerization of vinyl monomers in the presence of such unsaturated linear polyester resin components, low molecular weight polyester resin components are vinyl-based with a vinyl resin component having a large molecular weight and high linearity as the main chain. A hybrid resin component having a molecular structure branched from the resin component can be obtained. Furthermore, the acid group and the hydroxyl group in the hybrid resin having this branched structure form an ester bond between molecules to form a gel component.

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

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

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

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

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

  And diols represented by the formula (B);

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

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

  These unsaturated dicarboxylic acids may be added at a ratio of 0.1 to 10 mol% (preferably 0.3 to 5 mol%, more preferably 0.5 to 3 mol%) with respect to the total acid component of the polyester monomer. preferable. When the unsaturated dicarboxylic acid is added in this range, the unsaturated group concentration in the low molecular weight polyester molecule is optimal. When the amount of unsaturated dicarboxylic acid is less than 0.1 mol%, the polyester resin component and the vinyl resin component are not easily hybridized, and the effect of improving the fixability and developability is hardly obtained. When the amount of unsaturated dicarboxylic acid is more than 10 mol%, the number of unsaturated groups contained in one molecule of the polyester resin increases, so the vinyl resin that hybridizes with one molecule of the polyester resin increases, and the molecular weight between crosslinking points decreases. Gel component tends to be hard. As a result, the fixing property is deteriorated, or the gel component is sheared by kneading at the time of toner formation, and the high temperature offset resistance is deteriorated.

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

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

  The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%. The trivalent or higher polyvalent component is preferably 0.1 to 60 mol% in all components.

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

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

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

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

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

  Examples of the monomer for obtaining the vinyl resin component include the following.

  For example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Styrene derivatives such as styrene; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene and isoprene; Vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; Acetic acid Vinyl esthetics such as vinyl, vinyl propionate and vinyl benzoate Class: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Ter, vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N- such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. Vinyl compounds; vinyl naphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in admixture of two or more monomers.

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

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

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

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

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

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate) , 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); di-linked by an alkyl chain containing an ether bond Acrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene (2 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds are replaced with methacrylate. Polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). 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 1 part by mass or less, preferably 0.001 to 0.05 parts by mass with respect to 100 parts by mass of other vinyl monomer components.

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

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

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

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

  Furthermore, these polyfunctional polymerization initiators can be used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner.

  In particular, it is preferable to use in combination with a polymerization initiator having a half-life of 10 hours lower than the decomposition temperature for obtaining a half-life of 10 hours of the polyfunctional polymerization initiator.

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

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

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

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

  The binder resin used in the present invention has an acid value of 0.1 to 50 mgKOH / g (preferably 1 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g), and a hydroxyl value of 5 to 80 mgKOH / g (preferably The range of 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g) is preferable from the viewpoint of the ease of controlling the circularity by the chargeability of the toner and appropriate mechanical strength.

  The acid value of the binder resin is determined, for example, by the following operations 1) to 5). The basic operation belongs to JIS K0070.

  1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the content of components other than the binder resin in the sample is obtained. Weigh accurately 0.5 to 2.0 g of pulverized magnetic toner or binder resin. The mass of the binder resin component at this time is defined as W (g).

  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 an ethanol solution of 0.1 mol / l KOH, measurement is performed using a potentiometric titrator. For this titration, for example, an automatic titration using a potentiometric titration measuring device AT-400 (winworkstation) of Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.

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

5) Calculate the acid value according to the following formula. In the following formula, f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  The OH value is determined by, for example, the following operations 1) to 8). Basic operation conforms to JIS K0070.

  1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the content of components other than the binder resin in the sample is obtained. 0.5 to 2.0 g of the pulverized toner or binder resin is precisely weighed in a 200 ml flat bottom flask.

  2) Add 5 ml of acetylating reagent (25 g of acetic anhydride in a total volume flask (100 ml), add pyridine to bring the total volume to 100 ml and stir well). If the sample is difficult to dissolve, add a small amount of pyridine, or dissolve by adding xylene or toluene.

  3) Place a small funnel in the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.

  4) After 1 hour, remove from the glycerin bath to the flask, allow to cool, add 1 ml of water from the funnel and shake to decompose acetic anhydride.

  5) To complete the decomposition further, the flask is again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and flask wall are washed with 5 ml of ethanol.

6) Add a few drops of phenolphthalein solution as an indicator, titrate with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and end when the indicator is light red for about 30 seconds.

  7) Perform 2) to 6) as blank tests without adding resin.

8) Calculate the OH number by the following formula.
A = [{(BC) × 28.05 × f} / S] + D
(However, A is a hydroxyl value (mgKOH / g), B is the amount (ml) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test, and C is 0.5 kmol used for titration. / M ^{3 of} potassium hydroxide ethanol solution (ml), f is a factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution, and S is the amount of binder resin (g) contained in the sample. Yes, D is the acid value of the sample, where “28.05” is the formula weight of potassium hydroxide (56.11 × 1/2))

  The acid value and hydroxyl value of the binder resin can be adjusted by, for example, the types of monomers constituting the binder resin and their blending amounts.

  In the present invention, other resins such as rosin, modified rosin, aliphatic or alicyclic hydrocarbon resin can be mixed with the above-described binder resin as necessary. When two or more kinds of resins are mixed and used as a binder resin, as a more preferable form, those having different molecular weights are preferably mixed at an appropriate ratio.

  The number average molecular weight and the weight average molecular weight of the binder resin are determined by dissolving the binder resin in tetrahydrofuran (THF) and measuring the solution by gel permeation chromatography (GPC), and measuring the count number (retention time). ) And logarithmic values of a calibration curve prepared using several types of monodisperse polystyrene standard samples. Further, the molecular weight of the binder resin can be adjusted by polymerization conditions, use of a crosslinking agent, kneading of the binder resin, and the like.

  The glass transition temperature of the binder resin is generally such that the theoretical glass transition temperature described in the publication Polymer Handbook 2nd edition III-p139 to 192 (John Wiley & Sons) is 45 to 80 ° C. It can adjust by selecting the constituent material (polymerizable monomer) of resin. The glass transition temperature of the binder resin can be measured according to ASTM D3418-82 using a differential scanning calorimeter, for example, DSC-7 manufactured by PerkinElmer or DSC2920 manufactured by TA Instruments Japan. When the glass transition temperature of the binder resin is lower than the above range, the toner may have insufficient storability. When the glass transition temperature of the binder resin is higher than the above range, the toner may have insufficient fixability. It may become.

  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. By using the one-component development method, a carrier is unnecessary, which is advantageous in terms of downsizing the apparatus.

  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 ferromagnetic materials have an average particle size of 2 μm or less, preferably 0.05 to 0.5 μm. Further, the magnetic characteristics when 795.8 kA / m is applied are coercive force of 1.6 to 12.0 kA / m, saturation magnetization of 50 to 200 Am ² / kg (preferably 50 to 100 Am ² / kg), and residual magnetization of 2 to 20 Am. Those of ² / kg are preferred.

  These ferromagnetic materials are contained in the toner in an amount of about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 100 parts by weight of the resin component.

In particular, the content is preferably adjusted so that the true density of the toner particles is 1.50 or more and 2.00 (g / cm ³ ). When the true density of the toner particles is within this range, the surface modification of the toner particles is easily performed uniformly. The reason for this is not clear, but in the surface reforming apparatus described later, the circulation property of the toner particles in the apparatus is important. It is considered that the circulation of the toner particles can easily work efficiently, so that the circularity and the modification degree in different particle size regions can be easily made uniform, and the object of the present invention can be easily achieved.

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

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

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

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

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

  The toner of the present invention can be used as a two-component developer in combination with a carrier, and conventionally known carriers can be used as a carrier in the two-component development method. Specifically, particles having an average particle diameter of 20 to 300 μm, such as surface oxidized or unoxidized metals such as iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof, are 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.

  Moreover, in this invention, it is preferable to add and use a charge control agent. The charging property of the magnetic toner of the present invention may be positive or negative. However, since the binder resin itself has a high negative charging property, it is preferably a negatively charging toner.

  For example, organometallic complexes and chelate compounds are effective as negatively charged ones. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; metal complexes of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids and their metals. Examples thereof include salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Preferred examples of the charge control agent for negative charging include Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-. 84, E-88, E-89 (Orient Chemical).

  Examples of those that are controlled to be positively charged include modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like. Onium salts such as phosphonium salts and the like, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybthenic acid, phosphotungstomolybthenic acid, tannic acid, Lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyl Rusuzuboreto, be mentioned, such as organo-tin borate of dicyclohexyl tin borate. These can be used alone or in combination of two or more.

  Preferred examples of the charge control agent 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.) and Copy Blue PR (Clariant).

  These metal complex compounds can be used alone or in combination of two or more. The use amount of these charge control agents is preferably 0.1 to 5.0 parts by mass per 100 parts by mass of the binder resin from the viewpoint of the charge amount of the toner.

  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 average primary particle size is preferably in the range of 0.001 to 2 μm, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm.

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

  Furthermore, as the fluidity improver used in the present invention, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferable to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30 to 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. A total of 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver is used with respect to 100 parts by mass of toner.

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

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

  The method for producing the toner of the present invention is shown below, but is not particularly limited, and can be produced by a known method.

  For example, the toner of the present invention is prepared by sufficiently mixing a binder resin and other materials such as a magnetic material or other colorant, wax, and charge control agent by a mixer such as a Henschel mixer or a ball mill. , Using a heat kneader such as a kneader or extruder to melt, knead, and knead to make the resins compatible with each other, disperse or dissolve the magnetic particles, pigment or dye, cool and solidify, and then grind Then, after the surface modification step, an external additive such as an inorganic fine powder is mixed by the mixer. If necessary, a classification step may be further performed either before or after the surface modification step.

  Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauter mixer, turbulizer, cyclomix (made by Hosokawa Micron); Pacific Kiko Co., Ltd.); Redige mixer (manufactured by Matsubo) and the like.

  As a kneading machine, KRC kneader (manufactured by Kurimoto Iron Works); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactured by Mitsui Mining Co., Ltd.); MS pressure kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe Steel) can be used.

  As a pulverizer, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industry Co., Ltd.); Super Rotor (Nisshin Engineering).

  Classifiers include: Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron) An elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), a dispersion separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.), YM micro cut (manufactured by Yaskawa Shoji Co., Ltd.) and the like.

  As a sieving device used for sieving coarse particles, Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (manufactured by Deoksugaku Kogyo Co., Ltd.); Vibrasonic system (manufactured by 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 weight average particle diameter (D4) can be measured using a Coulter Multisizer II (trade name, manufactured by Coulter, Inc.), which is a particle diameter measuring machine. For example, measurement can be performed by connecting a number distribution and volume distribution interface (manufactured by Nikka) and a personal computer to the Coulter Multisizer II.

  In the present invention, the weight average particle diameter (D4) of the toner is preferably 4.0 μm to 9.0 μm from the viewpoint of compatibility between developability and fixability, and more preferably 4.5 μm to 8.0 μm. More preferably, it is 5.0 μm to 7.5 μm. When the thickness is less than 4.0 μm, developability such as fog tends to be deteriorated. If it exceeds 9.0 μm, the concentration tends to be thin.

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

  The sample to be tested is 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, as a dispersing agent in 100 to 150 ml of the electrolytic solution, and further 2 to 20 mg of toner is added. It can be prepared by dispersing for 3 minutes. In the measurement of the weight average particle diameter (D4) by the Coulter multisizer, a 100 μm aperture can be used as the aperture.

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

  The weight average particle diameter (D4) of the toner can be adjusted by, for example, pulverizing / classifying the toner or mixing a classified product having an appropriate particle diameter.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

(Binder resin production example)
(Polyester resin production example 1)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.390 mol
・ Fumaric acid 0.010 mol
・ Dodecenyl succinic anhydride 0.170 mol
Tetrabutyl titanate 0.1 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 ° C., peak molecular weight = 7800, number average molecular weight = 4600, Mw / Mn = 2.1, acid value = 5, hydroxyl value = 37).

(Polyester resin production example 2)
Unsaturated polyester resin P-2 (Tg 60 ° C., peak molecular weight = 4500, number average molecular weight = 2900, Mw / Mn = 5.4) in the same manner as in polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. Acid value = 27, hydroxyl value = 69).
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.370 mol
・ Isophthalic acid 0.290 mol
・ Fumaric acid 0.080 mol
・ Dodecenyl succinic anhydride 0.200 mol
・ Trimellitic acid 0.060 mol

(Polyester resin production example 3)
Saturated polyester resin P-3 (Tg 56 ° C., peak molecular weight = 7500, number average molecular weight = 5100, Mw / Mn = 2.4, except that the polyester monomer is mixed in the following ratio) Acid value = 5, hydroxyl value = 41) was obtained.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.400 mol
・ Dodecenyl succinic anhydride 0.170 mol

(Hybrid resin production example 1)
Unsaturated polyester resin P-1: 75 parts by mass, vinyl monomer as styrene: 18 parts by mass, butyl acrylate: 6.5 parts by mass, monobutyl maleate: 0.5 parts by mass, initiator as 2,5 -Dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128.4 ° C): 0.08 parts by mass were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 20 hours, the temperature was further raised to 150 ° C. and held for 5 hours to polymerize the unreacted vinyl monomer to obtain a hybrid resin. This is designated as binder resin 1. This resin had a main peak molecular weight of 7200 in the GPC molecular weight distribution of THF-soluble matter, contained 8 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 21 mass% of tetrahydrofuran-insoluble matter. . 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. The main peak molecular weight of the hydrolysis residue was 140000.

(Hybrid resin production example 2)
Unsaturated polyester resin P-2: 55 parts by mass, vinyl monomer as styrene: 30 parts by mass, butyl acrylate: 15 parts by mass, initiator as 2,5-dimethyl-2,5-bis (t-butyl Peroxy) hexyne-3: 0.15 part by mass was mixed. A hybrid resin was obtained using this vinyl monomer / polyester resin mixture in the same manner as in Hybrid Resin Production Example 1. This is designated as binder resin 2. This resin had a main peak molecular weight of 4300 in a GPC molecular weight distribution of THF-soluble matter, contained 37 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 41 mass% of tetrahydrofuran-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. The main peak molecular weight of the hydrolysis residue was 90000.

(Hybrid resin production example 3)
Saturated polyester resin P-3: 75 parts by weight, vinyl monomer as styrene: 18 parts by weight, butyl acrylate: 7 parts by weight, initiator as 2,5-dimethyl-2,5-bis (t-butyl par Oxy) hexyne-3: 0.08 part by mass was mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 20 hours, the temperature was further raised to 150 ° C. and held for 5 hours to polymerize the unreacted vinyl monomer, whereby a binder resin 3 was obtained. This resin had a main peak molecular weight of 7500 in the GPC molecular weight distribution of THF-soluble matter, contained 28 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained no tetrahydrofuran-insoluble matter.

(Hybrid resin production example 4)
Saturated polyester resin P-3: 75 parts by weight, vinyl monomer as styrene: 18 parts by weight, butyl acrylate: 7 parts by weight, initiator as 2,5-dimethyl-2,5-bis (t-butyl par Oxy) hexyne-3: 0.08 part by mass was mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 20 hours, the temperature was further raised to 150 ° C. and held for 5 hours to polymerize the unreacted vinyl monomer, whereby a binder resin 4 was obtained. This resin had a main peak molecular weight of 7500 in the GPC molecular weight distribution of THF-soluble matter, contained 28 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained no tetrahydrofuran-insoluble matter.

(Hybrid resin production example 5)
Saturated polyester resin P-3: 75 parts by weight, vinyl monomer as styrene: 18 parts by weight, butyl acrylate: 7 parts by weight, initiator as 2,5-dimethyl-2,5-bis (t-butyl par Oxy) hexyne-3: 0.08 part by mass was mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 20 hours, the temperature was further raised to 150 ° C. and held for 5 hours to polymerize the unreacted vinyl monomer, whereby a binder resin 5 was obtained. This resin had a main peak molecular weight of 7500 in the GPC molecular weight distribution of THF-soluble matter, contained 28 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained no tetrahydrofuran-insoluble matter.

(Example of styrene acrylic resin production)
Into a four-necked flask, 300 parts by mass of xylene is charged, heated to reflux, and mixed with 80 parts by mass of styrene, 20 parts by mass of acrylate-n-butyl and 2 parts by mass of di-tert-butyl peroxide. Was dropped over 5 hours to obtain a low molecular weight polymer (L-1) solution.

  On the other hand, 180 parts by mass of degassed water and 20 parts by mass of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and then 75 parts by mass of styrene, 25 parts by mass of acrylic acid-n-butyl, 0.005 of divinylbenzene. A mixed solution of 0.1 part by mass and 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane (half-life 10 hours temperature; 92 ° C.) is added, stirred and suspended. It was. After sufficiently substituting the inside of the flask with nitrogen, the temperature was raised to 85 ° C. to polymerize, and after maintaining for 24 hours, 0.1 part by mass of benzoyl peroxide (half-life 10 hours temperature; 72 ° C.) was added, Furthermore, it was maintained for 12 hours to complete the polymerization of the high molecular weight polymer (H-1).

  25 parts by mass of the high molecular weight polymer (H-1) was added to 300 parts by mass of the homogeneous solution of the low molecular weight polymer (L-1), and after mixing well under reflux, the organic solvent was distilled off. A styrene-based binder resin 1 was obtained. The binder resin has an acid value and a hydroxyl value of 0 mgKOH / g, a Tg of 55 ° C., an Mw of 280,000, an Mn of 15,000, and a tetrahydrofuran insoluble content of 0% by mass. It was.

(Synthesis Example 1 of a wax having a hydroxyl group)
1,000 g of paraffin wax (Mn: 420) as a raw material was placed in a glass cylindrical reactor, and the temperature was raised to 140 ° C. while blowing a small amount (3.2 liters / minute) of nitrogen gas into the cylindrical reactor. After adding 26.1 g (0.41 mol) of mixed catalyst of boric acid / boric anhydride: 1.44 (molar ratio) to the cylindrical reactor, air (20 liter / min) and nitrogen (15 liter / min) Was carried out at 180 ° C. for 2 hours. After completion of the reaction, an equal amount of warm water (95 ° C.) is added to the reaction mixture, the reaction mixture is hydrolyzed, and left to stand to separate the hydrocarbon wax separated into the upper layer, and the separated hydrocarbon wax is removed. Washed with water to obtain wax 1. Wax 1 had a hydroxyl value of 58 mgKOH / g, an ester value of 13.0 mgKOH / g, an acid value of 6.8 mgKOH / g, a melting point of 74 ° C., Mn of 380, and a penetration at 25 ° C. of 11.

(Synthesis Examples 2 to 3 of Wax Having a Hydroxyl Group)
Waxes 2 and 3 were obtained in the same manner as in Synthesis Example A except that polyethylene wax (Mn: 820) and Fischer-Tropsch wax (number average molecular weight (Mn): 710) were used as raw materials and the synthesis conditions were changed.

(Ester wax example 4)
An ester wax mainly composed of stearyl stearate (melting peak temperature 62 ° C. in DSC measurement) was used.

(Acid-modified wax example 5)
A propylene-ethylene copolymer (propylene component 92%, acid value 4.0 mgKOH / g, DSC melting peak temperature 130 ° C.) modified with maleic anhydride was used.

(Non-polar wax examples 6 and 7)
Waxes having physical properties as shown in Table 1 were used as waxes 6 and 7.

(Synthesis Examples 8 to 12 of wax grafted with styrene or styrene acrylic polymer)
After adding 40 g of dicumyl peroxide as a reaction initiator to 500 g of styrene monomer, it was added dropwise to 1500 g of heat-melted Fischer-Tropsch wax with stirring and reacted for 4 hours to obtain modified wax 8.

  Modified waxes 9 to 12 were similarly obtained by changing the type of hydrocarbon wax, the ratio of styrene monomer, the type and ratio of unsaturated carboxylic acid monomer, the heating temperature, and the like. The ratios and characteristics are shown in Table 2.

(Magnetic toner production example 1)
-Binder resin 1: 100 parts by mass-Wax 1: 5 parts by mass-Magnetic iron oxide: 95 parts by mass (composition: Fe ₃ O ₄ , shape: spherical, average particle size 0.21 μm, magnetism at 795.8 kA / m characteristics; Hc = 5.4kA / m, σs = 83.8Am 2 /kg,σr=7.0Am 2 / kg)
-T-77 (manufactured by Hodogaya Chemical Co., Ltd.): 2 parts by mass The above raw materials were premixed with a Henschel mixer and then kneaded with a twin-screw kneading extruder set at 130 ° C and 200 rpm. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, and then the obtained coarsely pulverized product is subjected to air temperature so that the exhaust temperature becomes 50 ° C. using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.). The mixture was finely pulverized and classified using a multi-division classifier utilizing the Coanda effect to obtain particles 1 having a weight average particle diameter (D4) of 6.0 μm.

Further, 100 parts by mass of the magnetic toner particles 1 and 1.2 parts by mass of hydrophobic silica fine powder obtained by subjecting dry silica (BET: 200 m ² / g) to hexamethyldisilazane treatment and then dimethyl silicone oil treatment, Were mixed with a Henschel mixer to prepare Magnetic Toner 1.

(Magnetic toner production examples 2 to 11 and comparative toner production examples 1 to 3)
In the magnetic toner production example 1, in the same manner except that the resin and wax shown in the table were used, in the fine pulverization step and the classification step, the pulverization conditions and classification conditions were finely adjusted, and the magnetic toner 2 having different weight average particle diameters To 11 and Comparative toners 1 to 3 were obtained.

[Example 1]
[Evaluation 1: Fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 410 mm / sec. This external fixing device is temperature-regulated every 5 ° C. within the range of 140 to 220 ° C., and is developed on plain paper (90 g / m ² ) paper (solid toner development amount is set to 0.6 mg / cm ² ) The fixed image is fixed, and the obtained image is rubbed back and forth 5 times with sylbon paper with a load of 4.9 kPa. The fixing temperature is the point where the density reduction rate of the image density before and after the rubbing is 15% or less. did. The lower this temperature, the better the low-temperature fixability.

The criteria for determining low-temperature fixability are shown below.
A: Density reduction rate is 15% or less at 145 ° C.
B: Density reduction rate is 15% or less at 155 ° C.
C: Density reduction rate is 15% or less at 165 ° C.
D: Density reduction rate is greater than 15% at 165 ° C.

For high-temperature offset resistance, the process speed is set to 100 mm / sec, the temperature is adjusted every 5 ° C. within the range of 200 to 240 ° C., the unfixed image is fixed, and the stain due to the offset phenomenon on the image is visually confirmed. The generated temperature was defined as high temperature offset resistance. The higher this temperature, the better the high temperature offset resistance. The evaluation paper was plain paper (64 g / m ² ).

The criteria for determining high temperature offset resistance are shown below.
A: There is no dirt at 240 ° C.
B: Slightly soiled at 240 ° C., but completely unstained at 230 ° C.
C: Slightly soiled at 230 ° C., but not soiled at 225 ° C.
D: Dirt is noticeable at 225 ° C.

[Evaluation 2: Durable developability]
A commercially available LBP printer (Laser Jet 4300, manufactured by HP) was modified to obtain A4 size 65 sheets / minute.

  To this modified machine, the magnetic toner 1 obtained in the toner production example 1 is filled, and the toner carrying member has a magnet with a developing pole of 750 gauss inside, and the surface roughness Ra is 1.0 μm. A sleeve having a diameter of Φ20 was incorporated, and the contact pressure of the developing blade was increased by 50%. A modified process cartridge in which the capacity of the toner filling part was doubled was mounted.

Using this as an image tester, after leaving overnight in a high-temperature and high-humidity environment of 32.5 ° C. and 85% RH, a horizontal line pattern with a printing rate of 4% is taken as one sheet / job, and between jobs. A print durability test of 30,000 sheets was performed using A4 plain paper (75 g / m ² ) in a mode in which the machine was once stopped and the next job was started.

  The following evaluation was performed during this print durability test or after a durability test of 30,000 sheets.

  The image density was measured and evaluated by measuring the reflection density of a 5 mm square solid black image using an SPI filter with a Macbeth densitometer (Macbeth Co., Ltd.), which is a reflection densitometer.

  The evaluation standard of image density is shown below.

As a result of calculating the reduction rate of the reflection density after 30,000 sheets endurance with respect to 1000 sheets endurance,
A: The decrease rate is less than 3%.
B: The decrease rate is 3% or more and less than 5%.
C: The decrease rate is 5% or more and less than 10%.
D: The decrease rate is 10% or more.

The evaluation criteria for streaks are shown below.
A: No streak occurs after 30,000 sheets.
B: Some streaks occur up to 30,000 sheets.
C: Streaks occur up to 20,000 sheets.
D: Streaks occur up to 10,000 sheets.

[Evaluation 3: Preservability]
In a commercially available LBP printer (Laser Jet 4300, manufactured by HP), toner 1 was filled in a modified process cartridge in which the capacity of the toner filling portion was doubled.

  Thereafter, the cartridge was placed in an environmental test box at 45 ° C. and 90%, and after 24 hours, it was moved to an environmental test box at 25 ° C. and 60%. Then, after another 24 hours, it was put in an environmental test box at 45 ° C. and 90%. After repeating this operation 20 times, in an environment of 25 ° C. and 60%, it was incorporated into a remodeled machine of a commercially available LBP printer (Laser Jet 4300, manufactured by HP), an image output test was performed, and image density and fogging were evaluated. .

  The evaluation standard of image density is shown below.

Reflection density after 1000 sheets endurance is
A: 1.45 or more B: 1.30 or more and less than 1.45 C: 1.15 or more and less than 1.30 D: less than 1.15

  The fog was measured by printing two solid white sheets and measuring the second fog by the following method.

  Using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), the transfer material before and after the image formation is measured, and the reflection density worst value after the image formation is Ds, and the reflection average density of the transfer material before the image formation. Was taken as Dr, Ds-Dr was determined, and this was evaluated as the amount of fogging. Smaller numbers indicate less fog.

The evaluation criteria for fogging are shown below.
A: Less than 0.5.
B: 0.5 or more and less than 1.0.
C: 1.0 or more and less than 2.5.
D: 2.5 or more.

[Examples 2 to 11, Comparative Examples 1 to 3]
Evaluation was performed in the same manner as in Example 1 using each toner shown in Table 3. The results are shown in Table 4.

Claims (7)

In a toner containing a binder resin having at least a polyester unit and wax A and wax B,
The wax A has at least one polar group among a carboxyl group, a hydroxyl group, and an ester group,
A toner wherein the wax B is a modified hydrocarbon wax grafted with a styrene or styrene acrylic polymer. The binder resin contains at least a resin component having a polyester unit and a resin component having a vinyl copolymer unit,
The Sr is 5.0 to 50.0, where Sr (% by mass) is a ratio of a resin component having a vinyl copolymer unit in the binder resin. toner. 3. The toner according to claim 2, wherein when the ratio of the styrene-based or styrene-acrylic polymer in the wax B is Sw (mass%), Sw and the Sr satisfy the following two expressions at the same time.
Sw ≦ −2Sr + 100.0
5.0 ≦ Sw ≦ 70.0   4. The toner according to claim 1, wherein the DSC melting peak temperature of the wax A is lower than the DSC melting peak temperature of the wax B.   The toner according to claim 1, wherein the acid value of the wax A is 1.0 to 30.0 mg KOH / g.   6. The toner according to claim 1, wherein the wax A has a hydroxyl value of 5.0 to 100.0 mg KOH / g.   The toner according to any one of claims 1 to 6, wherein the wax B is a Fischer-Tropsch wax grafted with a styrene-based or styrene-acrylic polymer.