JP5631066B2 - Toner production method - Google Patents

Description

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

  Conventionally, polycondensation resins such as polyester resins and vinyl resins such as styrene resins are mainly used as toner binder resins. Polyester resins have excellent fixing properties, but they also have the disadvantages that it is difficult to achieve a high molecular weight and that a hot offset phenomenon tends to occur.

  In order to make up for this defect, if the polyester resin contains a cross-linking component to increase the melt viscosity of the resin and improve hot offset resistance, not only the fixability is impaired, but also the grindability during toner production deteriorates. End up.

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

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

In Patent Document 1, a weight-average molecular weight obtained by graft polymerization of an unsaturated polyester resin with a vinyl monomer is 8000 to 20000, a melt viscosity at 100 ° C. is 10 ^{4 to} 10 ⁶ poise, and a glass transition temperature is 50 to 75. A toner using a graft polymer having a temperature of 0 ° C. as a binder resin is disclosed.

  In these methods, since no α, β-unsaturated dicarboxylic acid ester monomer is contained, it is difficult to achieve both the performance and chargeability relating to the purpose of fixing of the present invention at a higher level, or polyester. Is low in terms of low-temperature fixability.

  In Patent Document 2, a non-linear polyester having a weight average molecular weight (Mw) of 5000 to 200000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3 to 50 is reacted with a vinyl polymer. The toner binder for electrophotography obtained by making it have disclosed is disclosed. In this method, since the vinyl polymer and the polyester polymer are hybridized by an ester reaction, it is necessary to perform the reaction at a high temperature in order to increase the hybridization rate, and the vinyl polymer may be decomposed by heat. is there. Since the ester reaction does not proceed sufficiently at a temperature at which the vinyl polymer does not decompose, it is difficult to achieve sufficient hybridization, and the fixing property, hot offset resistance and developability cannot be satisfied.

  In these inventions, the content of residual volatile components such as alcohol in the resin tends to increase. If the operation such as vacuum distillation is performed for a long time in order to remove these, along with alcohol removal, a crosslinked structure tends to be formed excessively, the tetrahydrofuran insoluble matter tends to be excessively increased, and the viscosity is likely to increase. Yes, low-temperature fixability was easy to deteriorate.

  Furthermore, due to the temperature / decompression degree distribution in the kettle, the viscosity and alcohol content were likely to be uneven within the same lot of resin, and the viscosity and THF insoluble content were likely to be non-uniform. As a result, the dispersion of the internal additive such as wax in the toner becomes insufficient, and the charging stability of the toner may be lowered.

  On the other hand, many techniques for removing residual monomers and oligomers in a resin using a thin film evaporator have been disclosed. For example, Patent Document 3 discloses a method for removing a volatile component using a thin film evaporator when removing a volatile component from a resin composition containing a styrene acrylic copolymer and a volatile component. Patent Document 4 discloses a technique in which urethane-modified polyester is passed through a thin film evaporator to remove xylene and used as a toner binder.

  However, these technologies do not mention a hybrid resin comprising a vinyl resin and a polyester resin obtained by copolymerizing an α, β-unsaturated dicarboxylic acid ester monomer, and has high fixing performance and developability. Resins that are compatible at various levels have not been achieved.

  As described above, the toner is required to have further improved fixing performance and development performance, and a more excellent toner production method is desired.

Japanese Patent Laid-Open No. 1-156759 Japanese Patent Laid-Open No. 11-153858 JP-A-8-41123 JP 2002-055521 A

  There is little unevenness in the same lot of binder resin, a low-temperature fixability, hot offset resistance and electrostatic offset resistance, and a toner production method that is excellent in maintaining chargeability even after being placed in a harsh environment. It is to provide.

The present invention uses a thin film evaporator to melt and knead the binder resin obtained through the step of distilling off volatile components, and a mixture containing at least a colorant, and coarsely pulverize the obtained kneaded product. In the method for producing a toner having at least a step of further pulverizing the obtained coarsely pulverized product by a pulverizing means,
The binder resin is
i) containing a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded;
i-1) The vinyl resin component is obtained by copolymerizing at least an α, β-unsaturated dicarboxylic acid ester monomer and another monomer,
i-2) The content of the unit derived from the α, β -unsaturated dicarboxylic acid ester monomer in the vinyl resin component is 0.1% by mass or more and 20.0% by mass based on the vinyl resin component. % Or less,
ii) The hydroxyl value is 8 mgKOH / g or more and 100 mgKOH / g or less,
The present invention relates to a toner manufacturing method.

  According to the present invention, it is possible to provide a method for producing a toner that is excellent in low-temperature fixability, hot offset resistance, and electrostatic offset resistance, and that is excellent in maintaining chargeability even after being placed in a harsh environment. is there.

It is the schematic which shows an example of the thin film evaporator of this invention.

  The present inventors have found that the intended effect of the present invention can be achieved by using the binder resin as described above.

  The binder resin used in the present invention contains a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded, and the vinyl resin component contains at least an α, β-unsaturated dicarboxylic acid ester. It is important that the monomer is obtained by copolymerization with other monomers.

  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. The dispersibility of raw materials (for example, low-polarity wax components) can be improved at the same time.

  In addition, by using a hybrid resin, it is easy to achieve both fixability and developability by having a polyester resin component advantageous for low-temperature fixability and a vinyl resin component advantageous for developability and hot offset resistance. .

  Furthermore, the vinyl resin component is a resin component obtained by copolymerizing an α, β-unsaturated dicarboxylic acid ester monomer and another monomer, and it is necessary in the present invention to go through a process using a thin film evaporator. It is.

  By using an α, β-unsaturated dicarboxylic acid ester monomer as the vinyl resin component, the molecular weight of the vinyl resin component is increased even in a short time due to its high reactivity, and the resin is efficiently insoluble in tetrahydrofuran. It is possible to form components (hereinafter referred to as THF-insoluble components), and to optimize the balance between low-temperature fixability and hot offset resistance.

  On the other hand, the resin using α, β-unsaturated dicarboxylic acid ester monomer is a part derived from α, β-unsaturated dicarboxylic acid ester monomer in the vinyl resin component, and a dealcoholization reaction takes place to produce an acid anhydride group It's easy to do. Since the acid anhydride group is highly reactive, when further heated, the hybrid resin of the present invention reacts with a hydroxyl group in the polyester to form a crosslinked structure.

  For reasons to be described later, it is preferable to sufficiently remove volatile components such as alcohol produced by the dealcoholization reaction. Therefore, after the resin polymerization, a vacuum distillation step is added, and in particular, if the vacuum distillation time is long (it may vary depending on the scale, for example, 10 hours or more), crosslinking by the bond between the acid anhydride group and the hydroxyl group described above Is easy to proceed.

  As a result, in particular, depending on the content of the α, β-unsaturated dicarboxylic acid ester monomer, the THF-insoluble matter tends to become excessively large, and when it is made into a toner, the low-temperature fixability may be deteriorated, or other materials The dispersibility of the toner may be reduced, and the charging stability of the toner may deteriorate. Further, along with this decrease in dispersibility, the dispersion of THF-insoluble matter is likely to deteriorate, and the hot offset resistance is hardly exhibited.

  In addition, if the distillation under reduced pressure is lengthened, the residual monomer due to decomposition production such as styrene tends to increase, which is not preferable.

  In addition, if the vacuum distillation time is long, there is a large non-uniformity due to the location in the kettle due to the temperature difference between the wall near the reaction kettle and the kettle center, and the ease of depressurization between the liquid level and the inside. Prone. In particular, as described above, in the case of a hybrid resin capable of forming a crosslinked structure by an esterification reaction while removing volatile components such as alcohol during the decompression process, if the decompression distillation time is lengthened, the heterogeneity depending on the location may occur. There was a tendency to become large.

  As a result of non-uniformity depending on the location, the viscosity and THF-insoluble content may vary depending on the sampling location even within the same resin lot. In this case, since the pulverization property when the resin is pulverized is different, the resin having a different pulverized particle size is likely to be segregated. As a result, in the melt-kneading process during the toner manufacturing process, the dispersion of the internal additives such as wax in the toner may be insufficient due to the fact that the feed amount to the kneader is difficult to stabilize. It tends to lead to a decrease in charging stability of the toner.

  In order to prevent such problems due to non-uniformity, it may be necessary to add a new process such as uniform blending, which is not preferable in terms of cost reduction.

  The pulverized particle size of the binder resin is preferably a volume average particle size of 10 to 350 μm from the viewpoint of ease of handling. The volume average particle diameter was measured by the method of JIS K0069.

  Sampling multiple times from an arbitrary position in the same lot, measuring the volume average particle size and calculating the coefficient of variation of the volume average particle size in the same sample, it is possible to judge the uniformity within the lot It is.

  The coefficient of variation of the volume average particle diameter is preferably 0.1 to 20.0%, more preferably 0.1 to 15.0%, still more preferably 0.1 to 10.0 from the viewpoint of uniformity within the lot. %.

  On the other hand, by using a thin film evaporator, volatile components such as alcohol can be efficiently removed. With the efficient removal of this alcohol, by passing the hybrid resin using the α, β-unsaturated dicarboxylic acid ester monomer through a thin film evaporator, a dealcoholization reaction is likely to occur compared to the vacuum distillation step, It is considered that an acid anhydride group is easily generated. Therefore, it is considered that the above hybrid resin using a thin film evaporator can retain many acid anhydride groups in the resin.

  In addition, it is important that the toner in the present invention has a step of melt-kneading a mixture containing at least a binder resin and a colorant.

  That is, by melt-kneading the resin of the present invention, which retains many acid anhydride groups, as a binder resin, in this melt-kneading step, the acid anhydride groups and hydroxyl groups react to form a moderately crosslinked structure in the toner. It is possible to form. In addition, since the cross-linking is performed while being mixed during melt-kneading, the above-described problem of non-uniformity is hardly caused, and high dispersibility of an internal additive such as THF insoluble matter and wax formed by cross-linking can be achieved. Conceivable.

  Furthermore, the present inventors have found that when the resin using the thin film evaporator as described above is converted into a toner through a melt-kneading process, the charging stability of the toner is easily improved.

  This is probably due to the high dispersibility of the internal additives as described above and the use of a thin film evaporator to leave more acid anhydride groups in the resin, resulting in more acid anhydride in the toner. This is presumed to be due to two factors that the group can be retained.

  Moreover, since it is not necessary to carry out vacuum distillation for a long time by using a thin film evaporator, the above-described problems are hardly caused.

  In the present invention, the formation of the above-mentioned crosslinked structure and the improvement of the charging stability are achieved by passing a hybrid resin using a specific amount of α, β-unsaturated dicarboxylic acid ester monomer through a thin film evaporator, and then a melt-kneading step. It is possible to achieve it only after going through.

  As described above, since the resin is likely to be insufficiently mixed in the vacuum distillation, cross-linking unevenness is liable to occur in some places, and in some places, the cross-linking proceeds excessively, resulting in excessive toner viscosity. Or THF insoluble matter tends to be excessive. Further, the acid anhydride group is also easily consumed, and as a result, the charging stability of the toner tends to be lowered.

  Further, after the resin polymerization, a vacuum distillation step of a relatively short time (which may vary depending on the scale, but within 5 hours, for example) may be added. In this vacuum distillation step, after the dealcoholization and the crosslinking reaction with the hydroxyl group of the polyester are advanced to form an appropriate THF-insoluble matter, the toner viscosity may be easily adjusted by using a thin film evaporator.

  When the resin as described above is converted into a toner, it is easy to achieve both developability and fixability. In particular, the electrostatic offset resistance is easily improved in the fixing performance. Although this reason is not certain, the present inventors presume that it is the influence of the high dispersibility of an internal additive as mentioned above, and an acid anhydride group.

  Electrostatic offset means that the semi-molten toner present in the paper recess is fixed when the paper with the unfixed toner image transferred passes through the fixing nip between the fixing film of the fixing device and the pressure roller. It is a phenomenon that flies to the film side and fixes to paper after one round of the film. This phenomenon becomes prominent in a low-temperature and low-humidity environment where the fixability is disadvantageous. In particular, this phenomenon becomes more prominent in isolated dot images that are difficult to work with adhesion between toners and are disadvantageous in terms of fixability to paper. In addition, it is difficult to occur in paper having high surface smoothness such as coated paper, but it is likely to occur in paper having large surface irregularities.

  As a result of the study by the present inventors, it has been found that when the toner charge amount on the paper is higher, the electrostatic attracting force is more likely to act on the paper, and as a result, the electrostatic offset is less likely to occur. That is, when the toner charge amount on the paper is reduced, the electrostatic offset tends to be deteriorated. Further, since the toner image on the paper is more prominent when the toner image is not completely melted, the toner fixing property tends to be disadvantageous, and the toner image tends to become prominent on a machine with a high process speed.

  Such problems relating to toner fixing on paper can also be reduced by controlling the fixing device configuration and fixing bias, but the countermeasures in the main body configuration are contrary to the cost reduction of the apparatus as described above. Therefore, it is not preferable.

  In particular, as will be described later, in the present invention, a hybrid resin containing a large amount of polyester is preferable from the viewpoint of the balance of fixing performance. As described above, since the electrostatic offset is likely to be deteriorated when the fixing property is disadvantageous, it is preferable to use polyester which is advantageous for the fixing property in terms of the electrostatic offset resistance. However, since the polyester-based resin component has more polar groups than the vinyl-based resin component, the charge amount is easily relaxed and the toner charge amount on the paper is likely to be reduced. Therefore, a hybrid resin containing a large amount of the polyester resin component is advantageous as a low-temperature fixability, but the electrostatic offset may be worsened as the polyester resin component is increased.

By containing an acid anhydride group in the binder resin can be determined by the absorption peak derived from an acid anhydride in an infrared absorption spectrum (around about 1750 cm ^-1 to 1850 cm ^-1) are observed.

  In addition, in the present invention, from the viewpoint of the formation of the above-described crosslinked structure and optimization of the amount of acid anhydride groups, the inclusion of units derived from α, β-unsaturated dicarboxylic acid ester monomers in the vinyl resin component It is important that the amount is 0.1% by mass or more and 20.0% by mass or less. More preferably, it is 0.2 mass% or more and 18.0 mass% or less, More preferably, it is 0.3 mass% or more and 15.0 mass% or less.

  When the content of the unit derived from the α, β-unsaturated dicarboxylic acid ester monomer is less than 0.1% by mass, the THF-insoluble matter is hardly formed, and the hot offset resistance tends to deteriorate. Further, since the amount of the acid anhydride group is reduced, the charging stability of the toner is likely to be lowered, the initial image density is likely to be lowered, and the image density after the durability test is liable to be lowered. In addition, fogging to non-image portions is likely to occur, and electrostatic offset is likely to deteriorate. When the content of the unit derived from the α, β-unsaturated dicarboxylic acid ester monomer exceeds 20.0% by mass, the THF-insoluble matter tends to be excessively increased, and the low-temperature fixability tends to be deteriorated. Further, the dispersibility of other materials is likely to deteriorate, the charging stability of the toner is likely to deteriorate, and the above-described problems are likely to occur.

  The content of the unit derived from the α, β-unsaturated dicarboxylic acid ester monomer can be measured by NMR, and can be adjusted by the amount of vinyl monomer charged when polymerizing the hybrid resin.

  In the present invention, the hydroxyl value of the binder resin is 8 mgKOH / g or more from the viewpoint of ease of crosslinking with acid anhydride groups, ease of formation of THF-insoluble matter, and toner chargeability. It is important that it is 100 mgKOH / g or less, more preferably 12 mgKOH / g or more and 85 mgKOH / g or less, more preferably 14 mgKOH / g or more and 60 mgKOH / g or less.

  When the binder resin has a hydroxyl value of less than 8 mgKOH / g, it is difficult to form a cross-link with an acid anhydride group and to form a THF-insoluble matter, which is not preferable from the viewpoint of hot offset resistance. In addition, the charging stability of the toner tends to decrease. When the hydroxyl value of the binder resin exceeds 100 mgKOH / g, the moisture adsorption property of the binder resin tends to be high, and the charging stability and electrostatic offset of the toner are likely to deteriorate.

  The binder resin in the present invention preferably contains 5.0% by mass or more and 40.0% by mass or less of THF-insoluble matter from the viewpoint of toner developability and hot offset resistance. More preferably, it is 6.0 mass% or more and 37.0 mass% or less, More preferably, it is 7.0 mass% or more and 35.0 mass% or less.

  When the THF-insoluble content is less than 5.0% by mass, developability and hot offset resistance are likely to deteriorate, and when the THF-insoluble content exceeds 40.0% by mass, the low-temperature fixability is easily deteriorated. Further, the dispersibility of other materials tends to deteriorate, and the charging stability of the toner tends to deteriorate. In addition, dispersion of the THF-insoluble matter in the toner is likely to deteriorate, and it is difficult to exhibit hot offset resistance.

  Furthermore, in the present invention, the binder resin preferably has a softening point of 100.0 ° C. or higher and 160.0 ° C. or lower from the viewpoint of achieving both low temperature fixability and hot offset resistance of the toner. More preferably, the softening point is 105.0 ° C or higher and 155.0 ° C or lower, and further preferably the softening point is 110.0 ° C or higher and 150.0 ° C or lower.

  When the softening point is less than 100 ° C., the hot offset resistance tends to deteriorate. When the softening point exceeds 160.0 ° C., the low-temperature fixability tends to deteriorate.

  In the present invention, the binder resin preferably has a small amount of volatile components such as alcohol, and in particular, the content of the alcohol having 1 to 6 carbon atoms is preferably 100 ppm or less. More preferably, it is 80 ppm or less, More preferably, it is 50 ppm or less.

  The alcohol content can be lowered by adjusting the vacuum distillation time or by the conditions of the thin film evaporator.

  When the alcohol content is more than 100 ppm, the chargeability of the toner tends to be hindered especially when the toner is exposed to a high temperature environment for a long time. As a result, when developing with toner stored in a harsh environment, the density tends to decrease, particularly in a high-temperature and high-humidity environment that is disadvantageous to the density. In addition, as described above, in the toner in which the effect of improving the charging stability due to the acid anhydride group is difficult to obtain, the density reduction tends to be particularly severe.

  The reason for this is not clear, but alcohols having 1 to 6 carbon atoms are likely to volatilize, and the alcohols volatilize in a high temperature environment, and in a sealed toner container or in a low temperature environment, It is thought that it adsorbs on the toner surface. Thereafter, when an image is formed using the toner, it is presumed that the alcohol component on the toner surface acts as a leakage site for charging. In particular, when a history that goes back and forth between a high temperature environment and a normal temperature environment is given, the amount of alcohol adsorbed on the surface will increase due to repeated volatilization and adsorption of alcohol, which may reduce the chargeability of the toner. Easy to grow.

  In particular, in the case of a hybrid resin containing a large amount of a polyester resin component, the decrease in concentration tends to be large. Probably, it is considered that a polyester resin component containing a large amount of polar groups is more likely to adsorb volatilized alcohol than a vinyl resin component.

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

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

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

As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1) 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.

  (3) is mentioned as a manufacturing method used especially preferably by this invention. Among them, those obtained by dissolving an unsaturated polyester resin capable of reacting with a vinyl monomer in a vinyl monomer and polymerizing a mixture of the polyester resin and the vinyl monomer by a bulk polymerization method are preferable.

  In bulk polymerization, the molecular weight of the vinyl resin component can be increased. Therefore, the polyester resin component is hybridized to the vinyl resin component having a large molecular weight, resulting in a gel structure having a large molecular weight and a large molecular weight between cross-linking points. It becomes possible to obtain.

  A toner containing a gel component that is detected as such a THF-insoluble component makes the gel component easy to move even with a small amount of heat at the time of fixing, and is compared with the case of containing a gel component having a low molecular weight between cross-linking points. Since the resin is easily softened by heat, the fixability is easily improved. Furthermore, such a gel component has a high molecular structure and is strong in shearing force. Since the gel component is less likely to be cut in the kneading process of the toner, the hot offset resistance can be improved. It is easy to achieve both fixability and hot offset resistance.

  In addition, since the bulk polymerization method does not require a step such as evaporation of the solvent as compared with the solution polymerization method, a binder resin can be obtained at a low cost. Also, compared with the suspension polymerization method, the dispersing agent can be obtained. Therefore, the toner has a great merit as a binder resin for toner, such as being able to obtain excellent developability with little influence on the chargeability of the toner and the like.

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

  The unsaturated polyester resin component used in the hybrid resin of the present invention has a molecular weight of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5,000 to 10,000) in the GPC molecular weight distribution of THF-soluble matter. A low molecular weight unsaturated polyester resin component having a main peak in the range 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 2,000, the developability tends to deteriorate, and if it exceeds 30,000, the low-temperature fixability tends to deteriorate.

  Further, the unsaturated polyester resin component used in the present invention has a number average molecular weight (Mn) of 2,000 to 20,000, preferably 3,000 to 10,000.

  When the number average molecular weight (Mn) is less than 2,000, a gel component is hardly generated in the hybrid resin, and hot offset resistance and development durability are likely to deteriorate. If the number average molecular weight (Mn) is greater than 20,000, the solubility of the unsaturated polyester resin component in the vinyl monomer is lowered, making it difficult to obtain a hybrid resin by bulk polymerization, and the polyester resin component and the vinyl resin The resin component may be separated or the chargeability of the toner may be deteriorated.

  The unsaturated polyester resin component used in the present invention preferably has a hydroxyl value of 8 to 110 mgKOH / g, preferably 12 to 90 mgKOH / g, more preferably 15 to 70 mgKOH / g.

  By setting the hydroxyl value of the unsaturated polyester resin component of the present invention within the above range, the hydroxyl value of the binder resin can be easily adjusted within the above range.

  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 component having this branched structure form an ester bond between molecules to form a gel component.

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

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

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

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

  And diols represented by the formula (B);

が挙げられる。

Is mentioned.

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

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

  These unsaturated dicarboxylic acids may be added at a ratio of 0.1 to 10 mol% (preferably 0.3 to 5 mol%, more preferably 0.5 to 3 mol%) with respect to the total acid component of the polyester monomer. preferable. When the unsaturated dicarboxylic acid is added in this range, the unsaturated group concentration in the low molecular weight polyester molecule is optimal. When the amount of unsaturated dicarboxylic acid is less than 0.1 mol%, the polyester resin component and the vinyl resin component are not easily hybridized, and the effect of improving the fixability and developability is hardly obtained. If the amount of unsaturated dicarboxylic acid is more than 10 mol%, the molecular weight between the crosslinking points becomes small and the gel component tends to be hard, so that the fixability is deteriorated, or the gel component is sheared by kneading at the time of toner formation and hot offset resistance Or get worse.

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

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

  Examples of the trivalent or higher polyvalent carboxylic acid component include pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, and their anhydrides, lower alkyl esters;

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

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

  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 performed in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 170 to 280 ° C. The reaction can be 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 tetraisopropyl titanate, dipotassium oxalate titanate, terephthalic acid titanate are particularly preferable. Potassium. At this time, it is particularly preferable to add an antioxidant (particularly a phosphorus-based antioxidant) as an anti-coloring agent for the binder resin and a co-catalyst (a magnesium compound is preferable, and magnesium acetate is particularly preferable) as a reaction accelerator.

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

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

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

  In particular, in the present invention, it is important to use an α, β-unsaturated dicarboxylic acid ester monomer. The α, β-unsaturated dicarboxylic acid ester monomer is, for example, an aliphatic unsaturated polyvalent carboxylic acid such as fumaric acid, maleic acid, itaconic acid or citraconic acid, or an aromatic unsaturated polyvalent carboxylic acid such as phenylene diacrylic acid. Examples include ester derivatives of carboxylic acids.

  More specifically, for example, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monopentyl maleate, monohexyl maleate, monoheptyl maleate, monooctyl maleate, monoallyl maleate, monoester maleate Phenyl, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, ethyl butyl maleate, ethyl octyl maleate, butyl octyl maleate, butyl hexyl maleate, pentyl octyl maleate, monomethyl fumarate, Monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monopentyl fumarate, monohexyl fumarate, monoheptyl fumarate, monooctyl fumarate, fuma Acid monoallyl, monophenyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, ethyl butyl fumarate, ethyl octyl fumarate, butyl octyl fumarate, butyl hexyl fumarate, pentyl fumarate Examples include octyl, monoethyl itaconate, diethyl itaconate, monobutyl itaconate, and dibutyl itaconate.

  In particular, in the present invention, α, β-unsaturated dicarboxylic acid is used from the viewpoint of ease of handling as a monomer and from the viewpoint of facilitating stabilization of toner charging by selecting a more reactive monomer. Monoesters are preferred. Furthermore, from the viewpoint of easily forming an anhydride group, maleic acid monoester or fumaric acid monoester is more preferable, and maleic acid monoester is more preferable. Of these, monobutyl maleate is particularly preferred from the viewpoints of reactivity with copolymerized styrene or acrylate monomers and ease of formation of acid anhydrides.

  Moreover, it is also possible to add a crosslinkable monomer as exemplified below.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate) , 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); di-linked by an alkyl chain containing an ether bond Acrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene (2 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds are replaced with methacrylate. Polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Polyfunctional crosslinkers include pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate. Alternatives: triallyl cyanurate, triallyl trimellitate and the like.

  These crosslinking agents are preferably used in an amount of 1 part by mass or less, preferably 0.001 to 0.05 parts by mass with respect to 100 parts by mass of 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, 1,3-bis- (t-butylperoxy Isopropyl) benzene, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, tris- (t -Butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n- Butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) has a polymerization initiation function such as two or more peroxide groups in one molecule such as propane, 2,2-t-butylperoxyoctane and various polymer oxides. In one molecule such as a polyfunctional polymerization initiator having a functional group, diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate, and t-butylperoxyisopropyl fumarate, Examples thereof include polyfunctional polymerization initiators having both a functional group having a polymerization initiation function such as an oxide group and a polymerizable unsaturated group.

  Of these, more preferred are di-t-butylperoxyhexahydroterephthalate, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, di-t-butylperoxyase. Rate and 2,2-bis- (4,4-di-t-butylperoxycyclohexane) propane, and t-butylperoxyallyl carbonate.

  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, in the polymerization step, It is preferably added after the half-life indicated by the polyfunctional polymerization initiator has elapsed.

  These initiators are preferably used in an amount of 0.05 to 2 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

  As described above, the binder resin of the present invention is preferably obtained by a bulk polymerization method in which a vinyl monomer is polymerized without using a solvent or the like in the presence of an unsaturated polyester resin component.

  In particular, a polymerization initiator having a 10-hour half-life temperature of 100 to 150 ° C. is used at a temperature lower than the 10-hour half-life temperature of the polymerization initiator until the polymerization rate reaches 80%, preferably 90%. It is preferable to conduct a polymerization reaction and increase the molecular weight of the vinyl resin component produced by bulk polymerization. Furthermore, when the polymerization rate reaches 80% (preferably 90%) or more, it is preferable to carry out the polymerization reaction at a temperature higher than the 10-hour half-life temperature to terminate the reaction.

  A preferred method for producing the binder resin of the present invention will be specifically described below.

  First, after mixing a vinyl monomer and an initiator with an unsaturated polyester resin, the vinyl monomer / polyester resin mixture is polymerized at 120 ° C. for 10 hours. The temperature is further raised to 150 ° C. and held for 3 hours to polymerize the unreacted vinyl monomer, and then the temperature is further raised to 180 ° C. and distilled under reduced pressure for 5 hours to carry out the crosslinking reaction and alcohol removal. Thus, a hybrid resin is obtained.

  Further, this hybrid resin is introduced into a thin film evaporator. The introduction may be performed by melting the already pulverized resin powder again or by directly introducing the molten hybrid resin after the production. After passing through the thin film evaporator, the resin is taken out and pulverized to obtain a hybrid resin.

  Below, the thin film evaporator in this invention is demonstrated.

  The thin film evaporator is not particularly limited as long as it is an apparatus that can decompress the resin as a thin film, but a preferred apparatus is illustrated in FIG.

  As shown in FIG. 1, the thin film evaporator includes a tank unit 10 and a rotating shaft 11 that rotates in the tank, and the rotating shaft 11 includes a stirring blade 12. Further, the thin film evaporator has a steam outlet 2, heating medium inlets 5 and 6, and heating medium outlets 3 and 4 that serve as a heating medium path for heating the tank 10.

  It is preferable that a plurality of stirring blades 12 are provided in the longitudinal direction of the rotating shaft 11 and have a certain degree of inclination in the circumferential direction.

  When the molten resin is introduced into the thin film evaporator from the inlet 1, the molten resin is uniformly dispersed on the inner wall surface of the tank 10 by the distributor 8.

  The distributor 8 and the agitating blade 12 are provided with a mechanism that always forcibly thins the film by rotating by being driven by an upper motor (not shown), which has a narrow clearance with the inner wall surface. Due to the rotating operation of the stirring blade 12, the molten resin thinned is forcibly transferred to the lower resin outlet 7 side while the surface layer portion is constantly updated. During this time, the molten resin is finally discharged from the outlet 7 through the screw 7 through the screw 7 while being decompressed and preferably heated in the tank 10.

  The atmospheric pressure in the tank 10 is preferably about 0.3 to 500 Torr, more preferably 0.5 to 200 Torr, still more preferably 1 to 100 Torr. When the atmospheric pressure is too low, the pressure resistance of the apparatus becomes a problem, and when the atmospheric pressure is too high, it is difficult to obtain the intended effect of the present invention.

  The tank 10 is preferably heated. In particular, it is preferable to heat at 50 to 250 ° C., more preferably 70 to 220 ° C., and still more preferably 90 to 200 ° C. When the heating temperature is less than 50 ° C., the intended effect of the present invention is difficult to obtain, and when the heating temperature exceeds 200 ° C., the resin tends to be decomposed.

  The thickness of the resin to be made into a thin film can be adjusted by the distance between the inner wall surface of the tank 10 and the stirring blade 12, but is preferably 1 to 5 mm, more preferably 2 to 4 mm.

  The binder resin thus obtained preferably has an acid value of 0.1 to 50 mgKOH / g in order to improve the developability of the toner.

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

  The toner of the present invention may contain a wax.

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

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

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

  The amount to be contained in the toner is 2 to 20 parts by weight, more preferably 2 to 15 parts by weight, and further preferably 2 to 2 parts by weight with respect to 100 parts by weight of the resin component from the viewpoint of the balance between fixing performance and developability. 10 parts by mass. Generally, the higher the content, the better the low-temperature fixability and hot offset resistance, but the toner chargeability and the developability associated therewith tend to deteriorate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Next, specific examples of the compound will be shown.

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

  Further, the general formula (4)

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

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

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

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

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

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

  As a method of incorporating a charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of use of these charge control agents is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. Examples of such fluidity improvers include fluorine resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, and fine powder titanium oxide. , Fine powder alumina, fine powder treated with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, zircon Examples thereof include double oxides such as strontium acid and calcium zirconate; calcium carbonate and carbonate compounds such as magnesium carbonate.

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

  In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. The 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 the toner.

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

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

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

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

  As a toner production apparatus, for example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Corporation); a ribocorn (manufactured by Okawara Seisakusho); a nauter mixer, a turbulizer, a cyclomix (Hosokawa Micron Corporation) A spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); a radige mixer (manufactured by Matsubo).

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

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

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

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

  The measurement of various physical properties according to the present invention will be described below.

(1) Measurement of molecular weight of THF soluble matter (resin peak molecular weight, number average molecular weight Mn)
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

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

  On the other hand, after the resin is dispersed and dissolved in THF and allowed to stand overnight, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Myshor Disc H-25-2 (manufactured by Tosoh Corporation)) can be used. ) And use the filtrate as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of the toner adjusted so that the resin concentration is 0.5 to 5 mg / ml as a sample concentration. An RI (refractive index) detector is used as the detector.

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

(2) Tetrahydrofuran (THF) insoluble content The binder resin is weighed, put into a cylindrical filter paper (for example, No. 86R size 28 × 10 mm, manufactured by Toyo Filter Paper Co., Ltd.), and applied to a Soxhlet extractor. Extraction is carried out for 6 hours or more under reflux using 200 ml of tetrahydrofuran as a solvent. 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 the extraction is completed, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the binder resin or toner.

When the toner contains a THF-insoluble component such as a magnetic substance or pigment other than the resin component, the mass of the toner put in the cylindrical filter paper is W ₁ g, and the mass of the extracted THF-soluble resin component is W ₂ When the weight of the THF-insoluble component other than the resin component contained in the toner is W ₃ g, the content of the THF-insoluble component of the resin component in the toner can be obtained from the following formula.
THF insoluble matter (mass%) = [{W ₁ − (W ₃ + W ₂ )} / (W ₁ −W ₃ )] × 100

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

(4) Measuring method of hydroxyl value of resin The hydroxyl value of the binder resin in the present invention can be measured as follows.

(A) Reagent (a) Acetylation reagent: Add 25 g of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. The acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(C) N / 2 potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. The orientation is performed according to JIS K8006.

(B) Operation 0.5 to 2.0 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. A small funnel is put on the mouth of the flask, and the bottom is immersed in a glycerin bath at 95 to 100 ° C. to heat the bottom. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was heated again in a glycerin bath for 10 minutes, allowed to cool, then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol was used with a phenolphthalein solution as an indicator. Titrate with solution. A blank test is performed in parallel with the main test.

(C) Calculation formula The hydroxyl value of the binder resin is calculated by the following formula.
A = {(B + C) × f × 28.05} / S + D
However,
A: Hydroxyl value of resin B: Amount used of N / 2 potassium hydroxide ethyl alcohol solution in blank test (ml)
C: Amount of use of N / 2 potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of N / 2 potassium hydroxide ethyl alcohol solution S: Mass of sample (g)
D: Acid value of resin

(5) Method for measuring softening point of resin This refers to the one measured by an elevated flow tester according to JIS K 7210. Specifically, a 1 cm ³ sample was heated at a heating rate of 4 ° C./min using an elevated flow tester (product name: CFT-500D, manufactured by Shimadzu Corporation), and 980 N / m ² (10 kg) by a plunger. / Cm ² ), a nozzle having a diameter of 1 mm and a length of 1 mm is pushed out, thereby drawing a plunger drop (flow value) -temperature curve, and the height of the S-curve is h. At this time, the temperature corresponding to h / 2 (the temperature at which half of the resin flows out) is defined as the softening point.

(6) Method for measuring glass transition point Tg of resin The glass transition point of the binder resin in the present invention is as follows using a differential scanning calorimeter (DSC measuring device), Q-1000 (manufactured by TA Instruments Japan). Therefore it can be done. As the glass transition point of the binder resin, a temperature at which an endothermic peak measured at a temperature rise II of the following temperature curve is detected is used.
Sample: 5-20 mg, preferably 10 mg
Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
Temperature drop I (180 ° C. → 10 ° C., temperature drop rate 10 ° C./min.)
Temperature increase II (10 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)

(7) Measurement of Residual Alcohol Content of Resin Measured by gas chromatography (GC) by the internal standard method under the following conditions.
Measurement device: GC-17A manufactured by Shimadzu Corporation
Measurement conditions 1) Column J-W SCIENTIFIC capillary column DB-WAX (30 m × 0.25 mm)
2) Sample concentration 200 mg of resin / 10 ml of acetone
3) Amount of implantation 4 μl
4) Helium 90kPa
5) INJ temperature 200 ° C
6) DET temperature 200 ° C
7) Temperature program 50 min for 2 min hold, 5 ° C / min to 165 ° C, 32 ° C / min to 220 ° C, 220 ° C for 29 min hold

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

(Binder resin production example 1)
Unsaturated polyester resin P-1 (bisphenol A propion oxide: 1.15 mol / terephthalic acid: 0.400 mol / isophthalic acid: 0.588 mol / fumaric acid: 0.0120 mol polycondensation. Tg 60 ° C., Peak molecular weight = 7700, number average molecular weight = 4600, acid value = 5, hydroxyl value = 40): 74.0 parts by mass, and vinyl monomer as styrene: 18.0 parts by mass, butyl acrylate: 6.0 mass Parts, monobutyl maleate: 2.0 parts by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128.4 ° C.) as an initiator: 0. 08 parts by mass were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize unreacted vinyl monomers to obtain a hybrid resin.

Furthermore, this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of EXEVA were as follows: resin thickness: 3 mm, jacket temperature setting: 180 ° C., stirring rotation speed: 250 rpm, and reduced pressure level: 1 Torr. The feed amount was 50 kg / m ² h.

  After passing through EXEVA, the resin was taken out and pulverized to obtain a hybrid resin. This is designated as binder resin 1.

  This resin had a hydroxyl value of 32, a tetrahydrofuran insoluble content of 20.0%, a softening point of 130.0 ° C., and an alcohol content of 25.0 ppm. In addition, the resin after passing through EVA was sampled at any time so as to divide the resin almost equally into 5 with respect to the total removal time, and the volume average particle diameter was measured for the five samples. As a result, the volume average particle size was 250 μm, and the variation coefficient of the volume average particle size was 9.4%.

(Binder resin production example 2)
In Binder Production Example 1, 74.0 parts by mass of unsaturated polyester resin P-1: 75.0 parts by mass, and as a vinyl monomer, styrene: 18.0 parts by mass, butyl acrylate: 6.0 masses Parts, monobutyl maleate: instead of 2.0 parts by mass, styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monoethyl maleate: 1.0 parts by mass In the same manner as in Resin Production Example 1, a binder resin 2 was obtained. Table 1 shows the physical properties of the binder resin 2.

(Binder resin production example 3)
In Binder Production Example 1, 74.0 parts by mass of unsaturated polyester resin P-1: 75.0 parts by mass, and as a vinyl monomer, styrene: 18.0 parts by mass, butyl acrylate: 6.0 masses Parts, styrene: 18.0 parts by weight, butyl acrylate: 6.5 parts by weight, monobutyl fumarate: 0.5 parts by weight instead of 2.0 parts by weight In the same manner as in Resin Production Example 1, a binder resin 3 was obtained. Table 1 shows the physical properties of the binder resin 3.

(Binder resin production example 4)
In Binder Resin Production Example 1, instead of unsaturated polyester resin P-1: 74.0 parts by mass, unsaturated polyester resin P-2 (bisphenol A propion oxide: 1.12 mol / terephthalic acid: 0.400 mol) / Isophthalic acid: 0.588 mol / Fumaric acid: 0.0120 mol of condensation polymerized Tg 61 ° C., peak molecular weight = 8200, number average molecular weight = 4800, acid value = 3, hydroxyl value = 15): 78.0 Instead of styrene: 18.0 parts by weight, butyl acrylate: 6.0 parts by weight, monobutyl maleate: 2.0 parts by weight, styrene: 17.0 parts by weight, Binder resin 4 was obtained in the same manner as in Binder Resin Production Example 1, except that butyl acrylate: 5.0 parts by mass and monoethyl fumarate: 0.1 parts by mass were used. Table 1 shows the physical properties of the binder resin 4.

(Binder resin production example 5)
In the binder resin production example 1, instead of the unsaturated polyester resin P-1: 74.0 parts by mass, the unsaturated polyester resin P-2: 78.0 parts by mass was used, and the vinyl monomer was styrene: 18. 0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2.0 parts by mass, styrene: 17.0 parts by mass, butyl acrylate: 5.0 parts by mass, monoethyl fumarate: 0 A binder resin 5 was obtained in the same manner as in the binder resin production example 1 except that 0.07 parts by mass were used. Table 1 shows the physical properties of the binder resin 5.

(Binder resin production example 6)
In Binder Resin Production Example 1, instead of unsaturated polyester resin P-1: 74.0 parts by mass, unsaturated polyester resin P-3 (bisphenol A propion oxide: 1.10 mol / terephthalic acid: 0.380 mol) / Isophthalic acid: 0.561 mol / fumaric acid: 0.00900 mol / polycondensation of 0.05 mol of dodecenyl succinic anhydride, Tg 58.5 ° C., peak molecular weight = 7900, number average molecular weight = 4600, acid value = 3, hydroxyl value = 12): 78.0 parts by mass, and as a vinyl monomer, styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2.0 parts by mass Instead, tie: 17.0 parts by weight, butyl acrylate: 5.0 parts by weight, monoethyl fumarate: 0.05 parts by weight In the same manner as in Preparation Example 1 to obtain a binder resin 6. Table 1 shows the physical properties of the binder resin 6.

(Binder resin production example 7)
In Binder Resin Production Example 1, instead of unsaturated polyester resin P-1: 74.0 parts by mass, unsaturated polyester resin P-4 (bisphenol A propion oxide: 1.18 mol / terephthalic acid: 0.400 mol) / Isophthalic acid: 0.290 mol / fumaric acid: 0.0100 mol / condensation-polymerized 0.300 mol of dodecenyl succinic anhydride, Tg 51.0 ° C., peak molecular weight = 4300, number average molecular weight = 3000, acid value = 20, hydroxyl value = 88): 80.0 parts by mass, and as a vinyl monomer, styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2.0 parts by mass Instead, styrene: 15.5 parts by mass, butyl acrylate: 4.5 parts by mass, monoethyl fumarate: 0.02 parts by mass were used except for binding. In the same manner as fat in Production Example 1, to obtain a binder resin 7. Table 1 shows the physical properties of the binder resin 7.

(Binder resin production example 8)
In Binder Resin Production Example 1, instead of unsaturated polyester resin P-1: 74.0 parts by mass, unsaturated polyester resin P-5 (bisphenol A propion oxide: 1.20 mol / terephthalic acid: 0.400 mol) / Isophthalic acid: 0.290 mol / fumaric acid: 0.0100 mol / condensation-polymerized 0.300 mol of dodecenyl succinic anhydride, Tg 50.0 ° C., peak molecular weight = 4200, number average molecular weight = 2900, acid value = 25, hydroxyl value = 106): 80.0 parts by mass, and as a vinyl monomer, styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2.0 parts by mass Instead, styrene: 15.5 parts by mass, butyl acrylate: 4.5 parts by mass, dibutyl maleate: 0.02 parts by mass were used. , Like in the binder resin production example 1, to obtain a binder resin 8. Table 1 shows the physical properties of the binder resin 8.

(Binder resin production example 9)
In Binder Resin Production Example 1, the unsaturated polyester resin P-1 is 60 parts by mass, and the vinyl monomer is styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2. Instead of 0 parts by mass, the same procedure as in Binder Resin Production Example 1 was used except that styrene: 25.5 parts by mass, butyl acrylate: 9.5 parts by mass, and monoethyl fumarate: 5.0 parts by mass were used. Binder resin 9 was obtained. Table 1 shows the physical properties of the binder resin 9.

(Binder resin production example 10)
In Binder Resin Production Example 1, the unsaturated polyester resin P-1 is 50 parts by mass, and the vinyl monomer is styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2. Instead of 0 parts by mass, the same procedure as in Binder Resin Production Example 1 was used, except that styrene: 31.5 parts by mass, butyl acrylate: 11.5 parts by mass, and monoethyl fumarate: 7.6 parts by mass were used. Thus, a binder resin 10 was obtained. Table 1 shows the physical properties of the binder resin 10.

(Binder Resin Production Example 11)
In Binder Resin Production Example 1, the unsaturated polyester resin P-1 is 50 parts by mass, and the vinyl monomer is styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2. Instead of 0 parts by mass, the same procedure as in Binder Production Example 1 was performed except that styrene: 32.0 parts by mass, butyl acrylate: 10.0 parts by mass, and monoethyl fumarate: 8.0 parts by mass were used. Binder resin 11 was obtained. Table 1 shows the physical properties of the binder resin 11.

(Binder Resin Production Example 12)
In Binder Resin Production Example 1, the unsaturated polyester resin P-1 is 50 parts by mass, and the vinyl monomer is styrene: 18.0 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 2. Instead of 0 parts by mass, styrene: 32.0 parts by mass, butyl acrylate: 8.0 parts by mass, monoethyl fumarate: 10.0 parts by mass Binder resin 12 was obtained. Table 1 shows the physical properties of the binder resin 12.

(Binder Resin Production Example 13)
In Binder Production Example 5, after the vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize the unreacted vinyl monomer. Further, the binder resin 13 was obtained in the same manner as in the binder resin production example 5 except that the crosslinking reaction and alcohol removal were performed by raising the temperature to 180 ° C. and reducing the pressure for 3 hours. Table 1 shows the physical properties of the binder resin 13.

(Comparative binder resin production example 1)
In Binder Resin Production Example 11, after the vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize the unreacted vinyl monomer. Further, a hybrid resin was obtained in the same manner as in the binder resin production example 11 except that the crosslinking reaction and alcohol removal were performed by raising the temperature to 180 ° C. and reducing the pressure for 4 hours.

  The resin was taken out without using EXEVA and pulverized to obtain a hybrid resin. This is designated as comparative binder resin 1. Table 1 shows the physical properties of the binder resin 1 for comparison.

(Comparative binder resin production example 2)
In Comparative Binder Resin Production Example 1, after polymerizing a vinyl monomer / polyester resin mixture at 120 ° C. over 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize unreacted vinyl monomers. Thereafter, the hybrid resin was obtained in the same manner as in Comparative Binder Resin Production Example 1 except that the temperature was further increased to 180 ° C. and the pressure was reduced for 15 hours to carry out the crosslinking reaction and alcohol removal. This is designated as comparative binder resin 2. Table 1 shows the physical properties of the binder resin 2 for comparison.

  The resin was taken out without using EXEVA and pulverized to obtain a hybrid resin. This is designated as comparative binder resin 1. Table 1 shows the physical properties of the binder resin 1 for comparison.

(Comparative binder resin production example 3)
As a vinyl monomer, 270 g of styrene, 60 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, and 14 g of azobisisobutyronitrile as a polymerization initiator are placed in a dropping funnel.

  780 g (2.23 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 76 g (0.28 mol) of isododecenyl succinic anhydride, 180 g (1.09 mol) of terephthalic acid, Trimerit 30 g (0.16 mol) of acid and 2 g (8.0 mmol) of dibutyltin oxide were placed in a flask, and while stirring at a temperature of 130 ° C., a vinyl monomer and a polymerization initiator were added dropwise from a dropping funnel over 4 hours. Polymerization of the system copolymer unit was performed. After aging for 6 hours while maintaining at 130 ° C., the temperature was raised to 220 ° C. to polymerize the polyester unit to obtain a hybrid resin.

Furthermore, this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of EXEVA were as follows: resin thickness: 3 mm, jacket temperature setting: 170 ° C., stirring rotation speed: 250 rpm, and reduced pressure level: 100 Torr. The feed amount was 50 kg / m ² h. After passing through EXEVA, the resin was taken out and pulverized to obtain a hybrid resin. This is designated as comparative binding resin 3. Table 1 shows the physical properties of the binder resin 3 for comparison.

(Comparative binder resin production example 4)
In Binder Resin Production Example 6, the unsaturated polyester resin P-3 is 50 parts by mass, and the vinyl monomer is styrene: 17.0 parts by mass, butyl acrylate: 5.0 parts by mass, monoethyl fumarate: 0.0. A comparative binder resin 4 was obtained in the same manner as in the binder resin production example 6 except that styrene: 38.0 parts by mass and butyl acrylate: 12.0 parts by mass were used instead of 05 parts by mass. . Table 1 shows the physical properties of the binder resin 4 for comparison.

(Comparative binder resin production example 5)
In Binder Production Example 8, the unsaturated polyester resin P-5 is 45.0 parts by mass, and vinyl monomers are styrene: 15.5 parts by mass, butyl acrylate: 4.5 parts by mass, dibutyl maleate: Similar to Binder Resin Production Example 8 except that styrene: 32.0 parts by mass, butyl acrylate: 11.0 parts by mass, and dibutyl maleate: 12.0 parts by mass were used instead of 0.02 parts by mass. Thus, a comparative binder resin 5 was obtained. Table 1 shows the physical properties of the binder resin 5 for comparison.

(Comparative binder resin production example 6)
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 acrylic resin was obtained.

Furthermore, this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of EXEVA were as follows: resin thickness: 3 mm, jacket temperature setting: 170 ° C., stirring rotation speed: 250 rpm, and reduced pressure level: 200 Torr. The feed amount was 50 kg / m ² h. After passing through EXEVA, the resin was taken out and pulverized to obtain a styrene acrylic resin. This is designated as comparative binder resin 6. Table 1 shows the physical properties of the binder resin 6 for comparison.

(Comparative binder resin production example 7)
In Binder Resin Production Example 6, instead of unsaturated polyester resin P-3, unsaturated polyester resin P-6 (bisphenol A propion oxide: 1.08 mol / terephthalic acid: 0.400 mol / isophthalic acid: 0.0. 588 mol / fumaric acid: polycondensation of 0.0120 mol, Tg 63.0 ° C., peak molecular weight = 8700, number average molecular weight = 5500, acid value = 2, hydroxyl value = 7): 78.0 parts by mass are used A comparative binder resin 7 was obtained in the same manner as in Binder resin production example 6 except that. Table 1 shows the physical properties of the binder resin 7 for comparison.

(Comparative binder resin production example 8)
In Binder Resin Production Example 8, instead of unsaturated polyester resin P-5, unsaturated polyester resin P-7 (bisphenol A propion oxide: 1.15 mol / terephthalic acid: 0.400 mol / isophthalic acid: 0.005%). 290 mol / fumaric acid: 0.0100 mol / condensation of 0.300 mol of dodecenyl succinic anhydride, Tg 51.0 ° C., peak molecular weight = 4400, number average molecular weight = 3200, acid value = 22, hydroxyl value = 103 ): A comparative binder resin 8 was obtained in the same manner as in Binder Production Example 8 except that 80.0 parts by mass were used. Table 1 shows the physical properties of the binder resin 8 for comparison.

(Comparative binder resin production example 9)
In Binder Resin Production Example 5, instead of unsaturated polyester resin P-2, saturated polyester resin P-8 (bisphenol A propion oxide: 1.15 mol / terephthalic acid: 0.400 mol / isophthalic acid: 0.500 Mol / dodecenyl succinic anhydride: polycondensation of 0.100 mol, Tg 55.0 ° C., peak molecular weight = 5200, number average molecular weight = 3500, acid value = 7, hydroxyl value = 15): 78.0 parts by mass A comparative binder resin 9 was obtained in the same manner as in Binder Resin Production Example 5 except that it was used. Table 1 shows the physical properties of the binder resin 9 for comparison.

(Comparative binder resin production example 10)
In Binder Production Example 8, after polymerization of the vinyl monomer / polyester resin mixture at 120 ° C. for 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize unreacted vinyl monomers. Further, a hybrid resin was obtained in the same manner as in Binder Resin Production Example 8 except that the temperature was further increased to 180 ° C. and the pressure was reduced for 15 hours to carry out the crosslinking reaction and alcohol removal.

  The resin was taken out without using EXEVA and pulverized to obtain a hybrid resin. This is designated as a comparative binder resin 10. Table 1 shows the physical properties of the binder resin 10 for comparison.

(Comparative binder resin production example 11)
In Comparative Binder Production Example 10, after polymerizing a vinyl monomer / polyester resin mixture at 120 ° C. over 10 hours, the temperature was further raised to 150 ° C. and held for 4 hours to polymerize unreacted vinyl monomers. Thereafter, the hybrid resin was obtained in the same manner as in Comparative Binder Resin Production Example 10 except that the temperature was further raised to 180 ° C. and the pressure was reduced for 4 hours to carry out the crosslinking reaction and the alcohol removal. This is referred to as a binder resin 11 for comparison. Table 1 shows the physical properties of the binder resin 11 for comparison.

[Example 1]
Binder resin 1 100 parts by mass Magnetite (average particle size 0.20 μm) 95 parts by mass Illustrated monoazo iron compound (1) 2 parts by mass Fischer-Tropsch wax (DSC peak temperature 103 ° C.) 5 parts by mass After premixing with a Henschel mixer, it was melt-kneaded by a twin-screw kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) set at 130 ° C. and 150 rpm. At this time, the feed amount was set to 15 kg / hr, and the load current value was adjusted to be 70A to 85A. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, then finely pulverized using a pulverizer using a jet stream, classified using a multi-division classifier utilizing the Coanda effect, and the weight average diameter (D4 ) A negatively charged magnetic toner of 6.5 μm was obtained. Toner 1 was obtained by adding 1.2 parts by mass of negatively chargeable hydrophobic silica to 100 parts by mass of this toner with a Henschel mixer. The toner 1 was evaluated for the following items.

[Evaluation 1: Low temperature fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 400 mm / sec. This external fixing device is temperature-controlled every 5 ° C. within the range of 140 to 220 ° C., and is developed on plain paper (90 g / m ² ) paper (solid toner development amount on paper set to 0.7 mg / cm ² ) TBD 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.

[Evaluation 2: Hot offset resistance test]
With regard to hot offset resistance, the process speed is set to 120 mm / sec, the temperature is adjusted every 5 ° C. within the range of 200 to 240 ° C., the unfixed image is fixed, and the stain due to the offset phenomenon on the image is visually confirmed. The generated temperature was defined as high temperature offset resistance. The higher this temperature, the better the high temperature offset resistance. The evaluation paper was plain paper (64 g / m ² ).

The criteria for determining hot 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 3: Anti-static offset]
Laser beam printer manufactured by Hewlett-Packard Company: An evaluator modified so that the fixing temperature of the fixing device of Laser Jet 3005 can be arbitrarily set and the process speed is 310 mm / sec was used.

Since electrostatic offset becomes more conspicuous in a low temperature environment where low-temperature fixability is disadvantageous, in a low-temperature low-humidity environment (15 ° C., 10% RH), the fixing temperature is lowered by 20 ° C., and the temperature is adjusted to a low-temperature low-humidity environment for 24 hours After outputting a 3 cm square isolated dot image (image density set to 0.5 to 0.6) on the left FOX RIVER BOND paper (75 g / m ² ) paper, the solid white portion below the dot image The level of generated electrostatic offset was judged visually.

The criteria for determining electrostatic offset resistance are shown below.
A: Cannot be confirmed visually.
B: It can be confirmed very slightly.
C: The offset part can be seen at a glance, but there is a part that is not offset.
D: A square of 3 cm square can be clearly confirmed.

[Evaluation 4: Durable developability]
Laser beam printer manufactured by Hewlett-Packard Company: Laser Jet3005 is modified to 55 sheets machine, and A4 size manuscript with A4 size image area ratio 1.8% in high temperature and high humidity (32 ° C, 80% RH) environment. An image output test was performed using a transfer paper having a size of 75 g / m ² , and solid black image density and fogging were measured when 100 sheets and 15,000 sheets were passed. More rigorous evaluation is possible by evaluating in a high-temperature and high-humidity environment that is disadvantageous to toner charging and durable developability.

  The image density was measured by measuring the reflection density using a SPI filter with a Macbeth densitometer (manufactured by Macbeth Co.), and the five-point average was calculated. The fog was calculated by comparing the whiteness of the transfer paper measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

[Evaluation 5: Developability after long-term storage at high temperature]
Laser beam printer manufactured by Hewlett-Packard: Laser Jet 3005 process cartridge was filled with toner 1, and the cartridge was placed in an environmental test box at 45 ° C. and 90%, and after 24 hours, 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 10 times, in a high-temperature and high-humidity (32 ° C., 80% RH) environment, it was incorporated into the Laser Jet 3005 remodeled machine used in Evaluation 4, and the same image output test as in Evaluation 4 was performed. The subsequent solid black image density was measured. More rigorous evaluation is possible by evaluating in a high-temperature and high-humidity environment, which is disadvantageous for toner charging.

[Examples 2 to 13 and Comparative Examples 1 to 11]
Toners 2 to 13 and comparative toners 1 to 11 were obtained in the same manner as in Example 1 except that binder resins 2 to 13 and comparative binder resins 1 to 11 were used instead of binder resin 1. Tested as in 1. The test results are shown in Table 2.

  1 resin inlet, 2 steam outlet, 3, 4 heat medium outlet, 5, 6 heat medium inlet, 7 resin outlet, 8 distributor, 9 screw, 10 tank, 11 rotating shaft, 12 stirring blade

Claims (6)

Using a thin film evaporator, the binder resin obtained through the step of distilling off the volatile components, and a mixture containing at least the colorant are melt-kneaded, the obtained kneaded material is coarsely pulverized, and the obtained coarse product is obtained. In the method for producing a toner having at least a step of further pulverizing the pulverized product with a pulverizing means
The binder resin is
i) containing a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded;
i-1) The vinyl resin component is obtained by copolymerizing at least an α, β-unsaturated dicarboxylic acid ester monomer and another monomer,
i-2) The content of the unit derived from the α, β -unsaturated dicarboxylic acid ester monomer in the vinyl resin component is 0.1% by mass or more and 20.0% by mass based on the vinyl resin component. % Or less,
ii) The hydroxyl value is 8 mgKOH / g or more and 100 mgKOH / g or less,
And a method for producing the toner.   The toner production method according to claim 1, wherein the binder resin contains a resin component insoluble in tetrahydrofuran of 5.0% by mass or more and 40.0% by mass or less.   The method for producing a toner according to claim 1, wherein the softening point of the binder resin is 100.0 ° C. or higher and 160.0 ° C. or lower.   4. The toner production method according to claim 1, wherein the α, β-unsaturated dicarboxylic acid ester monomer is an α, β-unsaturated dicarboxylic acid monoester. 5.   The method for producing a toner according to any one of claims 1 to 4, wherein the α, β-unsaturated dicarboxylic acid monoester is monobutyl maleate.   The toner production method according to claim 1, wherein the binder resin has an alcohol content of 1 to 6 carbon atoms of 100 ppm or less.

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