JP6528464B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to a toner for electrostatic charge image development.

  In recent years, for the purpose of speeding up of printing speed, reduction of environmental load, etc., reduction of thermal energy at the time of toner image fixing is required.

  As described above, in order to reduce heat energy at the time of toner image fixing, a technique capable of improving the low temperature fixing property of the toner is required, and as one of the means for achieving this, crystalline polyester having excellent sharp melt properties And other crystalline resins are used as the binder resin.

  For example, Patent Document 1 proposes an electrostatic charge image developing toner containing a binder resin containing a crystalline polyester resin and an amorphous resin. Thus, by mixing and using the crystalline polyester resin and the amorphous resin, when the melting point of the crystalline polyester resin is exceeded by the temperature history at the time of fixing, the crystal part melts, and the crystalline polyester resin and the amorphous polyester resin are not Low temperature fixing can be achieved by compatibilization with the crystalline resin. Further, in Patent Document 1, by setting the thermal characteristics of the crystalline polyester resin and the amorphous resin contained in the binder resin within a specific range, fixing at a lower temperature than before can be achieved.

  Further, Patent Document 2 and Patent Document 3 are disclosed as a technology of using a crystalline resin such as crystalline polyester as a binder resin. Patent Document 2 proposes a toner binder resin containing a hybrid resin which is a copolymer of a crystalline polyester resin and an amorphous resin and an amorphous resin. The binder resin for toner has a phase separation structure (sea-island structure) in which the hybrid resin is a matrix and the amorphous resin is a domain, and it is disclosed that the low-temperature fixability is excellent. Patent Document 3 discloses a toner fixed at low temperature by introducing a crystalline polyester resin into a binder resin containing a vinyl-based resin.

JP, 2006-251564, A International Publication No. 2006/135041 JP, 2011-197659, A

  According to the techniques disclosed in Patent Document 1, Patent Document 2 and Patent Document 3, a toner with good low-temperature fixability can be obtained. However, in the image forming technology using toner, it is required to improve not only low temperature fixability but also various characteristics such as image storability, charge uniformity and mechanical strength in a well-balanced manner. The techniques disclosed in Document 2 and Patent Document 3 do not satisfy all the above characteristics in a well-balanced manner.

  SUMMARY OF THE INVENTION It is an object of the present invention to provide a means which has an excellent low temperature fixing effect and improves image storability, charging uniformity and mechanical strength.

  The present inventors accumulated earnest research. As a result, a binder resin having a specific phase separation structure, including a hybrid crystalline polyester resin and an amorphous resin in which a crystalline polyester resin unit and an amorphous resin unit other than the polyester resin are chemically bonded to each other The inventors have found that the above-mentioned problems can be solved by using the thermal properties within a specific range, and have completed the present invention.

  That is, the above-mentioned subject is a toner for developing an electrostatic charge image containing a binder resin, and in the binder resin, a crystalline polyester resin unit and an amorphous resin unit other than the polyester resin are chemically bonded. And a hybrid crystalline polyester resin and an amorphous resin, wherein the hybrid crystalline polyester resin forms a dispersed phase, and the amorphous resin has a phase separation structure to form a continuous phase, and the toner differential Let Tm1 (° C.) be the temperature of the endothermic peak derived from the hybrid crystalline polyester resin in the first temperature rising process in scanning calorimetry, let ΔH1 (J / g) be the endothermic amount based on the endothermic peak, and raise the second time Assuming that the heat absorption amount based on the endothermic peak in the temperature process is ΔH 2 (J / g), electrostatic charge image fulfilling the relationship of the following formulas (1) and (2) It is solved by the image toner.

  According to the present invention, it is possible to provide a means having the excellent low temperature fixing effect and improving the image storage property, the charging uniformity and the mechanical strength.

  Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. Further, in the present specification, “X to Y” indicating a range means “X or more and Y or less”. Moreover, unless otherwise indicated, measurement of operation, a physical property, etc. is measured on the conditions of room temperature (20-25 degreeC) / 40 to 50% of relative humidity.

  One embodiment of the present invention is “A toner for developing an electrostatic charge image containing a binder resin, wherein the binder resin comprises a crystalline polyester resin unit and an amorphous resin unit other than a polyester resin. A hybrid crystalline polyester resin and an amorphous resin bonded to each other, and the hybrid crystalline polyester resin forms a dispersed phase, and the amorphous resin has a phase separation structure forming a continuous phase, Let Tm1 (° C.) be the temperature of the endothermic peak derived from the hybrid crystalline polyester resin in the first temperature rising process in differential scanning calorimetry of toner, and ΔH1 (J / g) be the endothermic amount based on the endothermic peak, 2 An electrostatic charge image satisfying the relationships of the above formulas (1) and (2), where ΔH 2 (J / g) is the heat absorption amount based on the endothermic peak in the second temperature rising process Developing toner.

  In the present specification, "toner for developing electrostatic charge image" may be simply referred to as "toner". In the present specification, "hybrid crystalline polyester resin" may be simply referred to as "hybrid resin".

  In the toner according to the present invention, as described above, the binder resin constituting the toner contains a hybrid resin and an amorphous resin, and these resins have a specific phase separation structure. In addition, the toner of the present invention has certain thermal properties.

  As described above, the crystalline polyester resin is effective for improving the low temperature fixability of the toner, but when it is combined with the amorphous resin, the toner may be plasticized to deteriorate the image storability. In such a case, it is effective to suppress the compatibility of the crystalline polyester resin with the amorphous resin. However, the present inventors have newly found a problem that when the compatibilization is suppressed as described above, the charging uniformity is particularly likely to be reduced. The toner having low charging uniformity has a disadvantage that the image density is not constant during the image formation and an image defect occurs. In addition, it was found that when the compatibilization is suppressed, the mechanical strength also tends to decrease. When the mechanical strength of the toner is not sufficient, the toner may be broken by mechanical stress particularly at high speed printing, which may cause toner scattering, which is not preferable.

  As described above, in the toner containing the crystalline polyester resin and the amorphous resin, when the compatibilization of the crystalline polyester resin is suppressed to obtain good image storability, sufficient charging uniformity and mechanical strength can be obtained. It is difficult to improve all physical properties in a well-balanced manner, because there is a trade-off relationship.

  On the other hand, since the crystalline polyester resin becomes difficult to be taken in the amorphous resin by suppressing the compatibilization of the crystalline polyester resin with the amorphous resin, the crystals exposed on the toner surface It was considered that the chargeability of the toner was deteriorated by the polyester resin and image defects were generated. The present invention is based on the idea that the above problems can be solved by making the crystalline polyester resin unit hard to be exposed to the surface in the toner by hybridizing the crystalline polyester resin and setting it as a specific phase separation structure. It came to complete.

  As described in Patent Document 1, when introducing a crystalline polyester resin into a binder resin containing an amorphous resin to improve low-temperature fixability, the crystalline polyester resin is a toner by enhancing the affinity between these resins. Although the image is taken in well, the plasticization of the resin in the fixed image is excessively progressing, and the image storability may not be secured. However, if the affinity between the resins is lowered to improve the image storability, the crystalline polyester resin is easily exposed on the surface of the binder resin, so the crystalline polyester resin itself is difficult to be charged or the charge is maintained. In some cases, the chargeability of the binder resin may be deteriorated due to the low ability to

  On the other hand, the toner of the present invention contains a hybrid resin in which a crystalline polyester resin unit and an amorphous resin unit other than a polyester resin are chemically bonded. The hybrid resin according to the present invention, as described above, has an amorphous resin unit other than the polyester resin in addition to the crystalline polyester resin unit, and thus has a good affinity with the amorphous resin contained in the binder resin. Become. As a result, the crystalline resin unit of the hybrid resin can be easily fitted to the amorphous resin constituting the binder resin. As a result, the crystalline polyester resin unit is easily taken into the binder resin and hardly exposed to the surface, whereby the charging uniformity is improved. Furthermore, since the hybrid resin has a dispersed phase (domain) and the non-crystalline resin forms a continuous phase (matrix), the exposure of the crystalline polyester resin unit to the toner surface is further suppressed, and the charging is further enhanced. It is believed that the uniformity improves.

  Furthermore, as in Patent Document 3, when the binder resin has a shape in which the crystalline polyester resin is coated with a vinyl resin, although the exposure to the toner surface can be suppressed, the interface between the crystalline polyester resin and the vinyl resin. It is believed that cracking occurs and mechanical strength decreases. However, in the present invention, as described above, since the crystalline polyester resin is not coated with the vinyl resin, and the hybrid resin is used, as described above, the crystalline polyester resin unit in the hybrid resin and the noncrystalline It becomes easy to be compatible with the organic resin, and the strength at the interface between the hybrid resin and the amorphous resin is improved. Therefore, it is presumed that the cracking at the interface between the hybrid resin and the amorphous resin is suppressed, and the mechanical strength is improved.

  In addition, the toner of the present invention satisfies the relationships of the above formulas (1) and (2). Here, the above equation (1) indicates that the value of ΔH 2 / ΔH 1 is large, and that the compatibility between the hybrid resin and the amorphous resin is suppressed at the time of heat fixing. Moreover, Formula (2) has shown that melting | fusing point of hybrid resin exists in the range of 55-80 degreeC.

  In the present invention, since the crystalline polyester resin is hybridized, the incorporation of the crystalline polyester resin (unit) into the toner can be improved without excessively increasing the affinity to the amorphous resin. . That is, since the crystalline polyester resin (unit) is well incorporated into the toner even in the region where the compatibility is suppressed to satisfy the above-mentioned formula (1), the charging uniformity and mechanical strength of the toner are secured. At the same time, the binder resin does not become too plastic, and in particular, adhesion between images can be suppressed even at high speed printing, and good image storability can be achieved.

  According to the prior art, the binder resin in which the compatibility between the crystalline polyester resin and the non-crystalline resin is suppressed may cause problems such as the low temperature fixing property, the mechanical strength and the deterioration of the charging uniformity. However, according to the present invention, as described above, while maintaining good low-temperature fixability by hybridizing a crystalline polyester resin and taking a specific phase separation structure, image storability, charging uniformity, mechanical The strength can be improved.

  Furthermore, the toner of the present invention satisfying the above formula (2) has good low-temperature fixability, and can be sufficiently softened at the time of heat fixing. Further, since the hybrid resin has the crystalline polyester resin unit and the amorphous resin unit, not only the control of the compatibility but also the improvement of the low temperature fixing property can be achieved.

  The above mechanism is speculation, and the present invention is not limited to the above mechanism.

  Hereinafter, the present invention will be described in detail.

The electrostatic image developing toner (toner) according to the present invention essentially includes a binder resin containing a hybrid crystalline polyester resin (hybrid resin) described in detail below and an amorphous resin. Then, the toner of the present invention satisfies the above formulas (1) and (2). At this time, the definitions in the formulas (1) and (2) are as follows;
Tm 1 (° C.): the temperature of the endothermic peak derived from the hybrid crystalline polyester resin in the first heating process in differential scanning calorimetry (DSC);
ΔH 1 (J / g): heat absorption based on the above endothermic peak;
ΔH 2 (J / g): Endothermic amount based on an endothermic peak derived from the hybrid crystalline polyester resin in the second temperature raising process.

  In addition, although the definition which concerns on said Tm1, (DELTA) H1 and (DELTA) H2 is as above-mentioned, more specifically, the value measured by the method as described in the following Example shall be employ | adopted.

  The larger the value of ΔH 2 / ΔH 1 shown in the above formula (1), the more the compatibility between the hybrid resin and the amorphous resin is suppressed, and the upper limit thereof is 1. Therefore, as in the above formula (1), when the value of ΔH2 / ΔH1 is larger than 0.95, the compatibility between the hybrid resin and the amorphous resin contained in the binder resin is suppressed. . Therefore, good image storability is maintained without plasticization even after heat fixation. On the other hand, when compatibility is suppressed, as described above, although the charging uniformity and mechanical strength may be reduced, the binder resin of the present invention is a hybrid resin containing an amorphous resin unit. And the affinity between the hybrid resin and the amorphous resin is good. Therefore, the charging uniformity and the mechanical strength can be improved in a well-balanced manner without impairing the image storability.

  Furthermore, if the value of ΔH2 / ΔH1 is larger than 0.95, the compatibility between the hybrid resin and the amorphous resin in the binder resin is suppressed, so that the plasticization of the amorphous resin is insufficient. As a result, low temperature fixability tends to be impaired. However, in the present invention, the amorphous resin can be appropriately softened by using the hybrid resin, so the low temperature fixability is also excellent.

  The value of ΔH2 / ΔH1 is preferably larger than 0.96 from the viewpoint of improving the image storability. On the other hand, from the viewpoint of improving the charging uniformity, the value of ΔH 2 / ΔH 1 is preferably less than 0.99, and more preferably less than 0.98. That is, 0.96 <ΔH2 / ΔH1 <0.99 is preferable, and 0.96 <ΔH2 / ΔH1 <0.98 is more preferable.

  The value of Tm1 shown in the above formula (2) is the melting point of the hybrid resin, and when the melting point is within the range of the above formula (2), the toner can be sufficiently softened, and the low temperature fixability is sufficient. Can be secured. From the viewpoint of improving various properties in a well-balanced manner, the value of Tm1 preferably satisfies the relationship of the following formula (3).

  Further, Tm1 is more preferably 78 ° C. or less. That is, it is still more preferable that 70 ≦ Tm1 ≦ 78.

<Binder resin>
The binder resin constituting the toner according to the present invention includes a hybrid crystalline polyester resin (hybrid resin) described in detail below and an amorphous resin. In the binder resin, the hybrid resin forms a dispersed phase (domain), and the non-crystalline resin has a phase separation structure forming a continuous phase (matrix). In addition, that the binder resin has a specific phase separation structure as described above means that, for example, the toner is colored with osmium tetraoxide or the like as needed, and a scanning electron microscope (SEM) observation or It can confirm by performing transmission electron microscope (TEM) observation etc.

  The formation of such a specific phase separation structure depends on the molecular structures of the hybrid resin and the amorphous resin, and the content of the resin. Therefore, in order to form the above-mentioned specific phase separation structure, the content of the hybrid resin constituting the binder resin is preferably 3% by mass or more and less than 60% by mass with respect to the total amount of the binder resin. Further, by setting the content in the above range, the effect of improving various physical properties by the addition of the hybrid resin can be easily obtained. In particular, from the viewpoint of further improving low-temperature fixability and charging uniformity, the content is more preferably 30% by mass or more and less than 50% by mass, and still more preferably 30% by mass or more and less than 45% by mass. As a method for isolating and extracting the hybrid resin from the toner, for example, the method described in Japanese Patent No. 3869 968 or the like (method using a Soxhlet extractor) can be adopted, and the content ratio is specified by this. Can.

  On the other hand, the content of the amorphous resin contained in the binder resin is preferably more than 40% by mass and 97% by mass or less with respect to the total amount of the binder resin. Further, the content of the amorphous resin is more preferably 50% by mass or more and 70% by mass or less, and more preferably 55% by mass or more and 70% by mass or less based on the total amount of the binder resin. The resin contained in the binder resin may contain a resin other than the hybrid resin and the amorphous resin, but preferably, the binder resin is made of a hybrid resin and an amorphous resin. Each of the hybrid resin and the amorphous resin will be described below.

(Hybrid crystalline polyester resin (hybrid resin))
The hybrid crystalline polyester resin (hybrid resin) is a resin in which a crystalline polyester resin unit and an amorphous resin unit other than the polyester resin are chemically bonded.

  In the above, the crystalline polyester resin unit refers to a portion derived from the crystalline polyester resin. That is, it refers to a molecular chain having the same chemical structure as that constituting the crystalline polyester resin. Moreover, the non-crystalline resin unit other than polyester resin refers to the part derived from non-crystalline resin other than polyester resin. That is, it refers to a molecular chain having the same chemical structure as that constituting an amorphous resin other than polyester resin.

  The weight average molecular weight (Mw) of the hybrid resin is preferably 5000 to 100000, and more preferably 7000 to 50000, from the viewpoint of obtaining both low-temperature fixability and excellent long-term storage stability with certainty. And 8000 to 20000 are particularly preferable. By setting the weight average molecular weight (Mw) of the hybrid resin to 100,000 or less, sufficient low temperature fixability can be obtained. On the other hand, by setting the weight average molecular weight (Mw) of the hybrid resin to 5000 or more, excessive progress of the compatibility between the hybrid resin and the amorphous resin during toner storage is suppressed, and the toners are fused to each other. It is possible to effectively suppress image defects due to

«Crystalline polyester resin unit»
The crystalline polyester resin unit is a portion derived from a known polyester resin obtained by the polycondensation reaction of a divalent or higher valent carboxylic acid (polyvalent carboxylic acid) and an alcohol having a second or higher valent (polyhydric alcohol) In a differential scanning calorimetry (DSC) of a toner, it refers to a resin unit having not a stepwise endothermic change but a clear endothermic peak. Specifically, the distinct endothermic peak means that the half-width of the endothermic peak is within 15 ° C. when measured at a temperature rising rate of 10 ° C./min in differential scanning calorimetry (DSC) described in the examples. It means the peak.

  The crystalline polyester resin unit is not particularly limited as long as it is defined above. For example, for a resin having a structure in which another component is copolymerized in the main chain of a crystalline polyester resin unit, or a resin having a structure in which a crystalline polyester resin unit is copolymerized in a main chain of other components If the toner to be contained exhibits a clear endothermic peak as described above, the resin corresponds to a hybrid resin having a crystalline polyester resin unit as referred to in the present invention.

  The crystalline polyester resin unit is produced from a polyvalent carboxylic acid component and a polyhydric alcohol component. At this time, the carbon number C (acid) of the polyvalent carboxylic acid component constituting the crystalline polyester resin unit and the carbon number C (alcohol) of the polyhydric alcohol component satisfy the relationships of the following formulas (4) to (6) Preferred.

  By using the polyvalent carboxylic acid and the polyhydric alcohol satisfying the above conditions, the above formulas ΔH1, ΔH2 and Tm1 can be easily adjusted so as to satisfy the relationships of the above formulas (1) and (2). The upper limit of the carbon number C (acid) of the polyvalent carboxylic acid component and the carbon number C (alcohol) of the polyhydric alcohol component is not particularly limited, but C (acid) is 20 or less and C (alcohol) is 20 or less It is preferable that

  By satisfying the above formula (4), the regularity of the molecular chain of the crystalline polyester resin unit is enhanced, and the crystallinity is further enhanced. Further, by satisfying the above formulas (5) and (6), the interaction between crystalline polyester resin units between different molecules is increased, and the crystallinity is further enhanced.

  In addition, when containing 2 or more types of polyhydric carboxylic acid components, let said C (acid) be carbon number of the polyhydric carboxylic acid component with most content. In the case of the same amount, the carbon number of the polyvalent carboxylic acid component having the largest carbon number is C (acid).

  Similarly, when two or more polyhydric alcohol components are contained, C (alcohol) is the carbon number of the polyhydric alcohol component having the highest content. In the case of the same amount, the carbon number of the polyvalent carboxylic acid component having the largest carbon number is C (alcohol).

  The number of valences of the polyvalent carboxylic acid component and the polyhydric alcohol component is preferably 2 to 3 and particularly preferably 2 respectively. , Dicarboxylic acid component and diol component) will be described.

  As the dicarboxylic acid component, aliphatic dicarboxylic acids are preferably used, and aromatic dicarboxylic acids may be used in combination. It is preferable to use a linear type aliphatic dicarboxylic acid. Using a linear type has the advantage of improving the crystallinity. The dicarboxylic acid component is not limited to one type, and two or more types may be mixed and used.

  Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid Acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid (dodecanedioic acid), 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 18-octadecane dicarboxylic acid etc. are mentioned, Moreover, these lower alkyl esters and an acid anhydride can also be used.

  Among the above aliphatic dicarboxylic acids, aliphatic dicarboxylic acids having 6 to 12 carbon atoms are preferable because the effects of the present invention are easily obtained as described above.

  Examples of aromatic dicarboxylic acids that can be used together with aliphatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. Can be mentioned. Among these, terephthalic acid, isophthalic acid and t-butyl isophthalic acid are preferably used from the viewpoint of easy availability and ease of emulsification.

  As a dicarboxylic acid component for forming a crystalline polyester resin unit, the content of aliphatic dicarboxylic acid is preferably 50 constituent mole% or more, more preferably 70 constituent mole% or more, and still more preferably It is 80 constituent mole% or more, and particularly preferably 100 constituent mole%. By setting the content of the aliphatic dicarboxylic acid in the dicarboxylic acid component to 50 constituent mol% or more, the crystallinity of the crystalline polyester resin unit can be sufficiently secured.

  Moreover, as a diol component, it is preferable to use aliphatic diol, and you may make diol other than aliphatic diol be contained as needed. As the aliphatic diol, it is preferable to use a linear type. Using a linear type has the advantage of improving the crystallinity. The diol component may be used alone or in combination of two or more.

  Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include octadecanediol and 1,20-eicosanediol.

  Among the aliphatic diols, the aliphatic diol is preferably an aliphatic diol having 2 to 12 carbon atoms, as described above, so that the aliphatic diol satisfies the above-mentioned formula (6). That is, aliphatic diols having 6 to 12 carbon atoms are more preferable.

  Examples of diols other than aliphatic diols that are optionally used include diols having a double bond and diols having a sulfonic acid group. Specifically, examples of the diol having a double bond include 2 And -butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like.

  As a diol component for forming a crystalline polyester resin unit, it is preferable that content of an aliphatic diol shall be 50 structural-mol% or more, More preferably, it is 70 structural-mol% or more, More preferably, 80 structural It is at least mol%, particularly preferably 100 constituent mol%. By setting the content of the aliphatic diol in the diol component to 50 constituent mol% or more, it is possible to secure the crystallinity of the crystalline polyester resin unit and to obtain excellent low temperature fixability to the manufactured toner. The glossiness is obtained in the finally formed image.

  The ratio of use of the diol component to the dicarboxylic acid component is such that the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the diol component and the carboxyl group [COOH] of the dicarboxylic acid component is 2.0 / 1. Is preferably from 0 to 1.0 / 2.0, more preferably from 1.5 / 1.0 to 1.0 / 1.5, and 1.3 / 1.0 to 1.0 / 1. Particularly preferred is 3. When the use ratio of the diol component to the dicarboxylic acid component is in the above range, the formulas ΔH1, ΔH2 and Tm1 can be easily adjusted to satisfy the relationships of the formulas (1) and (2).

  The method for forming the crystalline polyester resin unit is not particularly limited, and the unit is formed by polycondensing (esterification) the polyvalent carboxylic acid and the polyhydric alcohol using a known esterification catalyst. Can.

  Examples of catalysts usable in the production of crystalline polyester resin units include alkali metal compounds such as sodium and lithium; compounds containing a Group 2 element such as magnesium and calcium; aluminum, zinc, manganese, antimony, titanium, tin And metal compounds such as zirconium and germanium; phosphorous acid compounds; phosphoric acid compounds; and amine compounds. Specific examples of the tin compound include dibutyltin oxide, tin octylate, tin dioctylate, and salts thereof. Examples of titanium compounds include titanium alkoxides such as tetranormal butyl titanate, tetraisopropyl titanate, tetramethyl titanate and tetrastearyl titanate; titanium acylates such as polyhydroxytitanium stearate; titanium tetraacetylacetonate, titanium lactate, titanium triethanolamide And titanium chelates such as nitrate. As a germanium compound, germanium dioxide etc. can be mentioned. Further, as the aluminum compound, oxides such as polyaluminum hydroxide, aluminum alkoxide and the like can be mentioned, and tributylaluminate etc. can be mentioned. You may use these individually by 1 type or in combination of 2 or more types.

  The polymerization temperature is not particularly limited, but is preferably 150 to 250 ° C. The polymerization time is not particularly limited, but preferably 0.5 to 10 hours. During the polymerization, the reaction system may be depressurized if necessary.

  The content of the crystalline polyester resin unit is preferably more than 85% by mass and 97% by mass or less with respect to the total amount of the hybrid resin. Furthermore, the content is more preferably more than 90% by mass and 95% by mass or less, and still more preferably more than 91% by mass and 93% by mass or less. By setting it as the said range, sufficient crystallinity can be provided to hybrid resin. In addition, the component and content rate of each unit in hybrid resin can be specified, for example by NMR measurement and methylation reaction P-GC / MS measurement.

  Furthermore, in the crystalline polyester resin unit, in addition to the above-mentioned polyvalent carboxylic acid and polyhydric alcohol, it is preferable that a compound for chemically bonding to the non-crystalline resin unit described in detail below is also polycondensed. As described in detail below, the non-crystalline resin unit is preferably a vinyl resin unit, but it is preferable to use a compound which is addition-polymerized to such a resin unit. Therefore, it is preferable that the crystalline polyester resin unit is formed by further polymerizing a compound which is polycondensable with the above-mentioned polyvalent carboxylic acid and polyvalent alcohol and which has an unsaturated bond (preferably a double bond).

  As such compounds, for example, polyvalent carboxylic acids having a double bond such as methylene succinic acid, fumaric acid, maleic acid, 3-hexendiodic acid, 3-octenedioic acid, etc .; 2-butene-1, Examples thereof include polyhydric alcohols having a double bond such as 4-diol, 3-butene-1,6-diol, 4-butene-1,8 diol and the like.

  It is preferable that the content rate of the structural unit derived from the said compound in a crystalline polyester resin unit is 0.5-20 mass% with respect to the whole quantity of a crystalline polyester resin unit.

  Here, the hybrid resin includes, in addition to the crystalline polyester resin unit, an amorphous resin unit other than the polyester resin described in detail below. The hybrid resin may be in any form such as a block copolymer or a graft copolymer as long as it contains an amorphous resin unit other than the crystalline polyester resin unit and the polyester resin. It is preferable that it is united. By using a graft copolymer, the orientation of the crystalline polyester resin unit can be easily controlled, and sufficient crystallinity can be imparted to the hybrid resin.

  Further, from the above viewpoint, it is preferable that the crystalline polyester resin unit is grafted with an amorphous resin unit other than the crystalline polyester resin as a main chain. That is, the hybrid crystalline polyester resin is preferably a graft copolymer having an amorphous resin unit other than the polyester resin as a main chain and a crystalline polyester resin unit as a side chain.

  By setting it as the said form, orientation of a crystalline polyester resin unit can be raised more, and crystallinity of a hybrid resin can be improved. As a result, it becomes easy to obtain a hybrid resin having ΔH1 and ΔH2 satisfying the above-mentioned formula (1).

  The hybrid resin may further have a substituent such as a sulfonic acid group, a carboxyl group or a urethane group introduced. The introduction of the substituent may be in a crystalline polyester resin unit, or in an amorphous resin unit other than the polyester resin described in detail below.

«Amorphous resin unit other than polyester resin»
Amorphous resin units other than polyester resin (sometimes referred to simply as "amorphous resin unit" in the present specification) control the affinity between the amorphous resin and the hybrid resin that constitute the binder resin. Is an essential unit for By the presence of the amorphous resin unit, the affinity between the hybrid resin and the amorphous resin is improved, the hybrid resin is easily taken into the amorphous resin, and charging uniformity and the like can be improved. .

  The amorphous resin unit is a portion derived from an amorphous resin other than the crystalline polyester resin. The inclusion of the amorphous resin unit in the hybrid resin (and further in the toner) can be confirmed, for example, by specifying the chemical structure using NMR measurement, methylation reaction P-GC / MS measurement. .

  In addition, the amorphous resin unit does not have a melting point and has a relatively high glass transition temperature (Tg) when differential scanning calorimetry (DSC) is performed on a resin having the same chemical structure and molecular weight as the unit. It is a resin unit. At this time, for the resin having the same chemical structure and molecular weight as the unit, the glass transition temperature (Tg1) in the first temperature rising process in DSC measurement is preferably 30 to 80 ° C., particularly 40 to 65 ° C. Is preferred. In addition, a glass transition temperature (Tg1) can be measured by the method as described in an Example.

  The amorphous resin unit is not particularly limited as long as it is defined above. For example, for a resin having a structure in which another component is copolymerized in the main chain by an amorphous resin unit, or a resin having a structure in which an amorphous resin unit is copolymerized in a main chain consisting of other components If the toner to be contained has the above amorphous resin unit, the resin corresponds to the hybrid resin having the amorphous resin unit in the present invention.

  The non-crystalline resin unit is preferably made of a resin of the same type as the non-crystalline resin (that is, a resin other than the hybrid resin) contained in the binder resin. With such a form, the affinity between the hybrid resin and the amorphous resin is further improved, the hybrid resin is further easily taken into the amorphous resin, and the charging uniformity and the like are further improved. Also, it becomes easy to control the values of ΔH1 and ΔH2.

  Here, "homogeneous resin" means that characteristic chemical bonds are commonly included in the repeating unit. Here, the “characteristic chemical bond” is described in the Material and Material Research Organization (NIMS) material and material database (http://polymer.nims.go.jp/PoLyInfo/guide/jp/term_polymer.html). According to the "polymer classification" of That is, polyacrylic, polyamide, polyanhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazen, polysiloxane, polystyrene, polysulfide, polysulfone, polyurethane, polyurea Chemical bonds that constitute polymers classified by a total of 22 types of polyvinyl and other polymers are referred to as “characteristic chemical bonds”.

  In addition, “the same kind of resin” in the case where the resin is a copolymer is characteristic when the monomer species having the above-described chemical bond is used as a constituent unit in the chemical structure of a plurality of monomer species constituting the copolymer. Refers to resins that share common chemical bonds. Therefore, even when the characteristics of the resin itself are different from each other, or even when the molar component ratio of the monomer species constituting the copolymer is different from each other, the same kind of chemical bond can be shared as long as they have characteristic chemical bonds in common. It is regarded as resin.

  For example, a resin (or a resin unit) formed by styrene, butyl acrylate and acrylic acid, and a resin (or a resin unit) formed by styrene, butyl acrylate and methacrylic acid, have at least a chemical bond constituting polyacryl Because they have, they are the same kind of resin. To illustrate further, the resin (or resin unit) formed by styrene, butyl acrylate and acrylic acid, and the resin (or resin unit) formed by styrene, butyl acrylate, acrylic acid, terephthalic acid and fumaric acid As a common chemical bond, it has at least a chemical bond constituting polyacryl. Therefore, they are the same kind of resin.

  Although the resin component which comprises an amorphous resin unit in particular is not restrict | limited, For example, a vinyl resin unit, a urethane resin unit, a urea resin unit etc. are mentioned. Among them, a vinyl resin unit is preferable because it is easy to control the thermoplasticity.

  The vinyl resin unit is not particularly limited as long as it is obtained by polymerizing a vinyl compound, and examples thereof include acrylic acid ester resin units, styrene-acrylic acid ester resin units, and ethylene-vinyl acetate resin units. One of these may be used alone, or two or more of these may be used in combination.

  Among the above-mentioned vinyl resin units, styrene-acrylic ester resin units (styrene-acrylic resin units) are preferable in consideration of the plasticity at the time of heat fixation. Therefore, hereinafter, a styrene acrylic resin unit as an amorphous resin unit will be described.

The styrene acrylic resin unit is formed by addition polymerization of at least a styrene monomer and a (meth) acrylic acid ester monomer. The styrene monomer referred to here includes, in addition to styrene represented by the structural formula of CH ₂ CHCH—C ₆ H ₅ , one having a structure having a known side chain or a functional group in the styrene structure. In addition to the acrylic acid ester compound and methacrylic acid ester compound represented by CH ₂ CHCHCOOR (R is an alkyl group), the (meth) acrylic acid ester monomer referred to here is an acrylic acid ester derivative or methacrylic acid. It contains an ester compound having a known side chain or functional group in the structure of an ester derivative or the like.

  Specific examples of styrene monomer and (meth) acrylic acid ester monomer capable of forming styrene acrylic resin unit are shown below, but those usable for forming styrene acrylic resin unit used in the present invention Is not limited to the following.

  First, specific examples of the styrene monomer include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4- Dimethylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene and the like can be mentioned. These styrene monomers may be used alone or in combination of two or more.

  Moreover, as a specific example of the (meth) acrylic acid ester monomer, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate Acrylic acid ester monomers such as stearyl acrylate, lauryl acrylate and phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, Stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl meta Relate, methacrylic acid esters such as dimethyl aminoethyl methacrylate.

  In the present specification, the term "(meth) acrylic acid ester monomer" is a generic term for "acrylic acid ester monomer" and "methacrylic acid ester monomer". "Methyl acrylate" is a generic term for "methyl acrylate" and "methyl methacrylate".

  These acrylic acid ester monomers or methacrylic acid ester monomers may be used alone or in combination of two or more. That is, to form a copolymer using a styrene monomer and two or more acrylic acid ester monomers, and using a styrene monomer and two or more methacrylic acid ester monomers to form a copolymer It is possible to form a united body or to form a copolymer by using a styrene monomer and an acrylic acid ester monomer and a methacrylic acid ester monomer in combination.

  It is preferable that the content rate of the structural unit derived from the styrene monomer in an amorphous resin unit is 40-90 mass% with respect to the whole quantity of an amorphous resin unit. Moreover, it is preferable in the amorphous resin unit that the content rate of the structural unit derived from the (meth) acrylic acid ester monomer is 10 to 60 mass% with respect to the total amount of the amorphous resin unit. By setting it as such a range, it becomes easy to control the plasticity of hybrid resin.

  Furthermore, in the amorphous resin unit, it is preferable that, in addition to the styrene monomer and the (meth) acrylic acid ester monomer, a compound for chemically bonding to the crystalline polyester resin unit is also addition polymerized. . Specifically, it is preferable to use a compound which is ester-bonded to a hydroxyl group [-OH] derived from a polyhydric alcohol or a carboxyl group [-COOH] derived from a polyvalent carboxylic acid, which is contained in the above-mentioned crystalline polyester resin unit. Therefore, the amorphous resin unit is addition-polymerizable to the above-mentioned styrene monomer and (meth) acrylic acid ester monomer, and has a carboxyl group [-COOH] or hydroxyl group [-OH]. It is preferable to further polymerize the compound.

  Such compounds include, for example, compounds having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester; 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And compounds having a hydroxyl group such as polyethylene glycol mono (meth) acrylate.

  It is preferable that the content rate of the structural unit derived from the said compound in an amorphous resin unit is 0.5-20 mass% with respect to the whole quantity of an amorphous resin unit.

  The formation method of the styrene acrylic resin unit is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include an azo-based or diazo-based polymerization initiator and a peroxide-based polymerization initiator shown below.

  As an azo or diazo polymerization initiator, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1) -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  Examples of peroxide polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4 -Dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4-t-butylperoxycyclohexyl) propane, tris- (t-butylperoxy) triazine and the like.

  In the case of forming resin particles by emulsion polymerization, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, hydrogen peroxide and the like.

  The content of the amorphous resin unit is preferably 3% by mass or more and less than 15% by mass with respect to the total amount of the hybrid resin. Furthermore, the content is more preferably 5% by mass or more and less than 10% by mass, and further preferably 7% by mass or more and less than 9% by mass. By setting it as the said range, sufficient crystallinity can be provided to a hybrid resin, and the binder resin for satisfy | filling the relationship of said Formula (1) can be obtained. Note that ΔH 1 and ΔH 2 depend on the content ratio of the hybrid resin to the non-crystalline resin in the binder resin, the chemical structure of the crystalline polyester resin unit and the non-crystalline resin unit, etc. By setting the content ratio of the non-crystalline resin unit in the hybrid resin in the above range, a binder resin for satisfying the above formula (1) can be easily obtained.

«Method for producing hybrid crystalline polyester resin (hybrid resin)»
The method for producing a hybrid resin contained in the binder resin according to the present invention is a method capable of forming a polymer having a structure in which the crystalline polyester resin unit and the non-crystalline resin unit are molecularly bonded. There is no particular limitation. As a specific manufacturing method of a hybrid resin, the method shown below is mentioned, for example.

(1) Method of producing a hybrid resin by performing polymerization reaction in which an amorphous resin unit is polymerized in advance and a crystalline polyester resin unit is formed in the presence of the amorphous resin unit In this method, first, Amorphous resin unit is formed by addition reaction of monomers (preferably, styrene monomer and vinyl monomer such as (meth) acrylic acid ester monomer) constituting the above-mentioned amorphous resin unit. . Next, in the presence of the amorphous resin unit, the polyvalent carboxylic acid and the polyhydric alcohol are polymerized to form a crystalline polyester resin unit. At this time, a hybrid resin is formed by causing a condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol, and causing an addition reaction of a polyvalent carboxylic acid or a polyhydric alcohol to an amorphous resin unit.

  In the above-mentioned method, it is preferable to incorporate portions which can react with each other in the crystalline polyester resin unit or the amorphous resin unit. Specifically, at the time of formation of an amorphous resin unit, carboxy group [-COOH] or hydroxyl group [-OH] remaining in the crystalline polyester resin unit in addition to the monomer constituting the amorphous resin unit A compound having a site capable of reacting with and a site capable of reacting with an amorphous resin unit is also used. That is, the crystalline polyester resin unit may be chemically bonded to the amorphous resin unit by reacting this compound with the carboxy group [-COOH] or hydroxyl group [-OH] in the crystalline polyester resin unit. it can.

  Alternatively, when forming the crystalline polyester resin unit, a compound which is capable of reacting with a polyhydric alcohol or polyhydric carboxylic acid and has a site capable of reacting with an amorphous resin unit may be used.

  By using the above method, a hybrid resin having a structure (graft structure) in which a crystalline polyester resin unit is molecularly bonded to an amorphous resin unit can be formed.

(2) Method of forming a crystalline polyester resin unit and an amorphous resin unit respectively and combining them to produce a hybrid resin In this method, first, a polyvalent carboxylic acid and a polyvalent alcohol are condensed. React to form a crystalline polyester resin unit. Further, separately from the reaction system for forming the crystalline polyester resin unit, the monomers constituting the above-mentioned amorphous resin unit are polymerized to form an amorphous resin unit. At this time, it is preferable to incorporate portions where the crystalline polyester resin unit and the amorphous resin unit can react with each other. In addition, since the method of incorporating such a reactive site | part is as above-mentioned, the detailed description is abbreviate | omitted.

  Next, the crystalline polyester unit formed above is reacted with the non-crystalline resin unit to form a hybrid resin of a structure in which the crystalline polyester resin unit and the non-crystalline resin unit are molecularly bonded. it can.

  In addition, when the above reactive part is not incorporated in the crystalline polyester resin unit and the amorphous resin unit, a system in which the crystalline polyester resin unit and the amorphous resin unit coexist is formed, and A method may be employed in which a compound having a moiety capable of binding to the crystalline polyester resin unit and the amorphous resin unit is introduced. Then, a hybrid resin having a structure in which a crystalline polyester resin unit and an amorphous resin unit are molecularly bonded can be formed via the compound.

(3) Method of producing a hybrid resin by performing a polymerization reaction of forming a crystalline polyester resin unit in advance and forming an amorphous resin unit in the presence of the crystalline polyester resin unit In this method, first, A condensation reaction of polyvalent carboxylic acid and polyvalent alcohol is carried out to carry out polymerization to form a crystalline polyester resin unit. Next, in the presence of the crystalline polyester resin unit, the monomers constituting the amorphous resin unit are polymerized to form an amorphous resin unit. At this time, as in the case of the above (1), it is preferable to incorporate portions which can react with each other in the crystalline polyester resin unit or the amorphous resin unit. In addition, since the method of incorporating such a reactive site | part is as above-mentioned, the detailed description is abbreviate | omitted.

  By using the above method, a hybrid resin having a structure (graft structure) in which an amorphous resin unit is molecularly bonded to a crystalline polyester resin unit can be formed.

  Among the formation methods of (1) to (3), the method of (1) is easy to form a hybrid resin having a structure in which a crystalline polyester resin chain is grafted to an amorphous resin chain, and the production process is simplified. It is preferable because it can be done. In the method of (1), since the crystalline polyester resin unit is bonded after the amorphous resin unit is formed in advance, the orientation of the crystalline polyester resin unit tends to be uniform. Therefore, it is preferable because the hybrid resin suitable for the toner defined in the present invention can be surely formed.

(Amorphous resin)
The amorphous resin constitutes a binder resin together with the above-mentioned hybrid resin. The non-crystalline resin is not particularly limited, but is a resin having no melting point and having a relatively high glass transition temperature (Tg) when differential scanning calorimetry (DSC) is performed on the resin. . When the glass transition temperature in the first temperature rising process is Tg1 and the glass transition temperature in the second temperature rising process is Tg2 in DSC measurement, the Tg1 of the non-crystalline resin is 35 to 80 ° C. It is preferable that it is especially 45-65 degreeC. Moreover, it is preferable that it is 20-70 degreeC, and, as for Tg2 of the said non-crystalline resin, it is preferable that it is especially 30-55 degreeC. The glass transition temperatures (Tg1 and Tg2) can be measured by the methods described in the examples.

  It is preferable that the amorphous resin contains a resin component constituting the unit described in the section <Amorphous resin unit other than polyester resin>. That is, the amorphous resin is preferably a vinyl resin, a urethane resin, a urea resin or the like. Furthermore, the amorphous resin may be an amorphous polyester resin such as a styrene acrylic modified polyester resin.

  The amorphous resin contained in the binder resin is preferably composed of a resin of the same type as the amorphous resin unit of the hybrid resin. Here, "consisting of the same kind of resin" may be a form consisting only of the same kind of resin, or is a form containing not only the same kind of resin but other non-crystalline resin, It is also good. However, in the case of a form containing the same kind of resin and another amorphous resin, the content of the same kind of resin is preferably 15% by mass or more with respect to the total amount of amorphous resin, 20% by mass or more It is more preferable that

  Furthermore, the non-crystalline resin may be a copolymer having a unit derived from a resin of the same type as the non-crystalline resin unit of the hybrid resin and a unit derived from another non-crystalline resin. At this time, the copolymer may be any of a block copolymer, a graft copolymer and the like, but a graft copolymer is preferable from the viewpoint of easily controlling the compatibility with the hybrid resin. However, in this case, the content of a unit derived from a resin of the same type as the amorphous resin unit of the hybrid resin is preferably 15% by mass or more, and 20% by mass or more with respect to the total amount of amorphous resin. Is more preferable.

  In addition, since the definition which concerns on "the same kind of resin" was demonstrated in the term of the above-mentioned << amorphous resin unit other than a polyester resin >>, detailed description is abbreviate | omitted.

  Among the above resins, the resin used as the amorphous resin is preferably a vinyl resin or a styrene acrylic modified polyester resin, and particularly preferably a vinyl resin. The vinyl resin and the styrene acrylic modified polyester resin are easy to control the compatibility with the hybrid resin, particularly when the non-crystalline resin unit of the hybrid resin is a vinyl resin unit, and to control the values of ΔH1 and ΔH2 It is preferable in that.

  Therefore, the vinyl resin and the styrene acrylic modified polyester resin will be described below.

«Vinyl resin»
When a vinyl resin is used as the non-crystalline resin, the vinyl resin is not particularly limited as long as it is obtained by polymerizing a vinyl compound, but, for example, acrylic ester resin, styrene-acrylic ester resin, ethylene-vinyl acetate resin, etc. Can be mentioned. One of these may be used alone, or two or more of these may be used in combination.

  Among the above-mentioned vinyl resins, styrene-acrylic ester resin (styrene acrylic resin) is preferable in consideration of the plasticity at the time of heat fixation. As a monomer which comprises a styrene acrylic resin, the thing similar to the compound mentioned as a monomer which comprises a styrene acrylic resin unit in the term of said <non-crystalline resin unit other than polyester resin> can be used.

  Therefore, although a detailed description is omitted, as a styrene monomer, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene; ) As acrylic acid ester monomers, acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate It is preferable to use a methacrylic acid ester such as These styrene monomers and (meth) acrylic acid ester monomers may be used alone or in combination of two or more.

  In addition, other monomers may be polymerized, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl ester of maleic acid, mono itaconic acid, and the like. Alkyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. are mentioned.

  It is preferable that the content rate of the structural unit derived from the styrene monomer in a styrene acrylic resin is 40-90 mass% with respect to the whole quantity of a styrene acrylic resin. Moreover, it is preferable in the styrene acrylic resin that the content rate of the structural unit derived from the (meth) acrylic acid ester monomer is 10-60 mass% with respect to the whole quantity of a styrene acrylic resin. By setting it as such a range, it becomes easy to control the plasticity of amorphous resin.

  It is preferable that the content rate of the structural unit derived from the said other monomer in a styrene acrylic resin is 0.5-30 mass% with respect to the whole quantity of a styrene acrylic resin.

  The method for producing the styrene acrylic resin is not particularly limited, and the styrene acrylic resin can be produced by the same method as the method for forming a styrene acrylic resin unit described in the section of << noncrystalline resin unit other than polyester resin >>.

«Styrene acrylic modified polyester resin»
An amorphous styrene acrylic modified polyester resin may be used as the amorphous resin. Here, the "styrene acrylic modified polyester resin" refers to an amorphous polyester molecular chain (hereinafter, also referred to as a polyester segment) and a styrene acrylic copolymer molecular chain (hereinafter, also referred to as a styrene acrylic copolymer segment). It is a resin composed of polyester molecules of a molecularly bonded structure. That is, the styrene acrylic modified polyester resin is a resin having a copolymer structure in which a styrene acrylic copolymer segment is covalently bonded to a polyester segment.

  Here, the styrene acrylic modified polyester resin used as the amorphous resin is clearly distinguished from the above hybrid resin in the following points. That is, unlike the crystalline polyester resin unit constituting the above-mentioned hybrid resin, the polyester segment constituting the amorphous styrene acrylic modified polyester resin does not have a clear melting point and has a relatively high glass transition temperature (Tg). It is an amorphous molecular chain having Such can be confirmed by performing differential scanning calorimetry (DSC) on the toner. Moreover, since the monomer (chemical structure) which comprises a polyester segment differs from the monomer (chemical structure) which comprises a crystalline polyester resin unit, it can be distinguished also by analysis, such as NMR, for example.

  The polyester segment is formed of a polyhydric alcohol component and a polyhydric carboxylic acid component.

  The polyhydric alcohol component is not particularly limited, but is preferably an aromatic diol or a derivative thereof from the viewpoint of chargeability and toner strength, for example, bisphenols such as bisphenol A and bisphenol F, And ethylene oxide adducts of these, and alkylene oxide adducts of bisphenols such as propylene oxide adducts.

  Among them, it is preferable to use an ethylene oxide adduct and a propylene oxide adduct of bisphenol A as the polyhydric alcohol component, particularly from the viewpoint of improving the charging uniformity of the toner. These polyhydric alcohol components may be used alone or in combination of two or more.

  Examples of the polyvalent carboxylic acid component to be condensed with the polyvalent alcohol component include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalene dicarboxylic acid, etc .; fumaric acid And aliphatic carboxylic acids such as maleic anhydride and alkenylsuccinic acid; and lower alkyl esters of these acids, acid anhydrides and the like, and one or more of these can be used.

  The formation method of the polyester segment is not particularly limited, and the polyester segment can be produced by the same method as the formation method of the crystalline polyester resin unit described in the section of << crystalline polyester resin unit >>.

  The above-mentioned styrene acrylic copolymer segment is a molecular chain derived from the same monomer as the styrene acrylic resin unit described in the section of "Amorphous resin unit other than polyester resin" above. Therefore, the detailed description about the kind of monomer which comprises the said segment, a composition ratio, the formation method of the said segment, etc. is abbreviate | omitted.

  The content of the polyester segment in the styrene acrylic modified polyester resin is preferably 40 to 90% by mass with respect to the total amount of the styrene acrylic modified polyester resin. Moreover, it is preferable that the content rate of the styrene acrylic copolymer segment in a styrene acrylic modified polyester resin is 10-60 mass% with respect to whole quantity of a styrene acrylic modified polyester resin. By setting it as such a range, it becomes easy to control the plasticity of styrene acrylic denaturation polyester resin.

  The amorphous resin preferably has a weight average molecular weight (Mw) of 5000 to 150000, and more preferably 10000 to 70000, from the viewpoint of easily controlling its plasticity.

(Form of binder resin)
The binder resin contained in the toner of the present invention may have any form (form of resin particles) as long as it contains a hybrid resin and an amorphous resin.

  For example, a resin particle (binder resin particle) composed of a binder resin may have a so-called single layer structure, or a core-shell structure (a resin that forms a shell portion on the surface of the core particle) (Aggregated, fused form) may be used. The resin particle of core-shell structure has a resin region (shell portion) having a relatively high glass transition temperature on the surface of the resin particle (core particle) having a relatively low glass transition temperature containing a coloring agent, a wax, etc. Have.

  The core-shell structure is not limited to the one in which the shell part completely covers the core particle, and for example, the shell part does not completely cover the core particle, and the core particle is exposed in some places. Including those that exist.

  The cross-sectional structure of the core-shell structure can be confirmed, for example, using a known means such as a transmission electron microscope (TEM) or a scanning probe microscope (SPM).

  In the case of using resin particles of core-shell structure, the hybrid resin and the amorphous resin may be contained in either the core particle or the shell portion, but the chargeability is reduced due to the crystalline polyester resin unit. From the viewpoint of suppressing and further improving the charging uniformity, it is preferable that at least the hybrid resin be contained in the core particle. At this time, the amorphous resin may be contained in any of the core particle and the shell portion, but in the core particle, the hybrid resin and the amorphous resin are contained in the core particle, and the amorphous resin is contained in the shell portion. And particularly preferred. With such a form, in the core particle, the affinity between the hybrid resin and the non-crystalline resin is increased, and the hybrid resin is less likely to be exposed on the surface, thereby further improving the mechanical strength as well as the charging uniformity. be able to.

  The content of the core portion is preferably 30 to 95% by mass, where the total resin amount of the core portion and the shell portion is 100% by mass.

<Other ingredients>
In the toner of the present invention, in addition to the above-mentioned essential components, if necessary, internal additives such as releasing agents, colorants and charge control agents; external additives such as inorganic fine particles, organic fine particles and lubricants It may be done.

(Mold release agent (wax))
The release agent constituting the toner is not particularly limited, and known ones can be used. Specifically, for example, polyolefin wax such as polyethylene wax and polypropylene wax, branched hydrocarbon wax such as microcrystalline wax, paraffin wax, long chain hydrocarbon wax such as sasol wax, and distearyl ketone Dialkyl ketone wax, carnauba wax, montan wax, behenyl behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18- Ester-based waxes such as octadecanediol distearate, tristearyl trimellitate, distearyl maleate, ethylenediamine behenylamide, trimesterate tristearylamide And the like amide-based waxes such as.

  The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C. By setting the melting point within the above range, the heat resistant storage stability of the toner is secured, and stable toner image formation can be performed without causing cold offset even when fixing is performed at a low temperature. The content of the releasing agent in the toner is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.

<Colorant>
As a coloring agent which can constitute the toner, carbon black, magnetic substance, dye, pigment and the like can be optionally used, and as carbon black, channel black, furnace black, acetylene black, thermal black, lamp black and the like are used Be done. Magnetic materials include ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but exhibit ferromagnetism by heat treatment, For example, an alloy of the type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide and the like can be used.

  As a black coloring agent, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black and the like, and further magnetic powder such as magnetite and ferrite are used.

  As colorants for magenta or red, C.I. I. Pigment red 2, 3, 5, 6, 7, 15, 16, 16. 48: 1, 53: 1, 57: 1, 60, 63, 64, 68, and so on. 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 139, 144, 149, 150, 163, 166, 170, The same as 177, 178, 184, 202, 206, 207, 209, 222, 238, 269 and the like.

  Moreover, as a coloring agent for orange or yellow, C.I. I. Pigment oranges 31, 43, C.I. I. Pigment yellow 12, 14, 15, 17, 74, 83, 93, 94, 138, 155, 162, 180, 185 and the like.

  Further, as colorants for green or cyan, C.I. I. Pigment blue 2, 3, 15, 15, 2: 15, 15, 4: 16, 16, 17, 60, 62, 66, C.I. I. Pigment green 7 and the like.

  These colorants may be used alone or in combination of two or more as needed.

  A mixture of colorants may also be used in an amount of preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the entire toner. Within such a range, color reproducibility of the image can be ensured.

  Moreover, as a magnitude | size of a coloring agent, 10-1000 nm and 50-500 nm are preferable at a volume average particle diameter, and also 80-300 nm are especially preferable.

<Charge control agent>
As the charge control agent, various known compounds such as nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts and the like can be used. .

  The addition amount of the charge control agent is usually 0.1 to 10% by mass, preferably 0.5 to 5% by mass with respect to 100% by mass of the binder resin in the toner particles finally obtained. .

  The size of the charge control agent particles is preferably 10 to 1000 nm, 50 to 500 nm, and more preferably 80 to 300 nm in number average primary particle diameter.

<External additive>
From the viewpoint of improving the charging performance, the fluidity, or the cleaning property as a toner, particles such as known inorganic fine particles and organic fine particles and lubricant can be added to the surface of toner particles as an external additive.

  Preferred examples of the inorganic fine particles include inorganic fine particles of silica, titania, alumina, strontium titanate and the like.

  These inorganic fine particles may be hydrophobized if necessary.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, organic fine particles of homopolymers such as styrene and methyl methacrylate and copolymers of these can be used.

  The lubricant is used to further improve the cleaning property and transferability, and as the lubricant, for example, zinc of stearic acid, salts of aluminum, copper, magnesium, calcium and the like, zinc of oleic acid Salts of manganese, iron, copper, magnesium etc., salts of zinc of palmitic acid, salts of copper, magnesium, calcium etc., salts of linoleic acid zinc, calcium etc., salts of ricinoleic acid zinc, calcium etc. of higher fatty acids Metal salts are mentioned. Various external additives may be used in combination.

  The addition amount of the external additive is preferably 0.1 to 10.0% by mass with respect to 100% by mass of the toner particles.

  The external additive may be added using any of various known mixing devices such as a turbular mixer, a Henschel mixer, a Nauta mixer, and a V-type mixer.

[Toner for electrostatic image development (toner)]
The toner of the present invention has an average particle diameter of 3.0 to 8.0 μm, preferably 4.0 to 7.5 μm, as a volume average particle diameter. By being in the above range, toner particles with high adhesive strength which fly during fixing and adhere to the heating member and cause fixing offset are reduced, and transfer efficiency is enhanced to improve halftone image quality. Image quality such as thin lines and dots is improved. In addition, toner fluidity can be secured.

  The average particle diameter of the toner can be controlled by the concentration of the coagulant and the amount of the solvent added in the aggregation / fusion step at the time of production of the toner, the fusion time, and further the composition of the binder resin.

  From the viewpoint of improving the transfer efficiency, the toner for electrostatic image development of the present invention preferably has an average circularity of 0.92 to 1.000, and 0.940 to 0.995, as represented by Formula 1 below. It is more preferable that

  In addition, average circularity can be measured, for example using the measuring apparatus "FPIA-2100" (made by Sysmex) of average circularity.

<Method of Producing Toner of the Present Invention>
The method for producing the toner of the present invention is not particularly limited, and known methods such as kneading and pulverizing method, suspension polymerization method, emulsion aggregation method, dissolution suspension method, polyester elongation method, dispersion polymerization method may be mentioned.

  Among these, from the viewpoint of the uniformity of particle diameter, the controllability of the shape, and the easiness of formation of the core-shell structure, it is preferable to adopt the emulsion aggregation method. Hereinafter, the emulsion aggregation method will be described.

(Emulsification aggregation method)
In the emulsion aggregation method, a dispersion of resin fine particles (hereinafter also referred to as "resin fine particles") dispersed by a surfactant or a dispersion stabilizer is mixed with a dispersion of toner particle components such as colorant fine particles. A method of forming toner particles by performing aggregation between resin fine particles by aggregating until the particle diameter of a desired toner is obtained by adding an aggregating agent and thereafter or simultaneously with aggregation. .

  Here, the resin fine particles may be composite particles formed of a plurality of layers having a configuration of two or more layers made of resins having different compositions.

  The resin fine particles can be produced, for example, by an emulsion polymerization method, a mini emulsion polymerization method, a phase inversion emulsification method, or the like, or can be produced by combining several production methods. When the resin fine particles contain an internal additive, it is preferable to use a mini-emulsion polymerization method among them.

  When the internal additive is contained in the toner particles, the resin fine particles may contain the internal additive, or a dispersion liquid of the internal additive fine particle consisting only of the internal additive is separately prepared, and the internal addition is performed. The agent fine particles may be coagulated together when the resin fine particles are coagulated.

  Further, toner particles having a core-shell structure can also be obtained by the emulsion aggregation method, and specifically, the toner particles having a core-shell structure first coagulate the binder resin fine particles for the core particles and the colorant. (, Fusing) to produce core particles, and then adding binder resin fine particles for shell part to the dispersion of core particles, thereby aggregating binder resin fine particles for shell part on the surface of core particles, It can be obtained by forming a shell part which fuses and coats the core particle surface.

  When the toner is produced by the emulsion aggregation method, the method for producing the toner according to the preferred embodiment comprises the steps of preparing a hybrid crystalline polyester resin fine particle dispersion and a non-crystalline resin fine particle dispersion (hereinafter also referred to as preparation step) (a And (b) mixing and affixing / fusing the hybrid crystalline polyester resin fine particle dispersion and the non-crystalline resin fine particle dispersion (hereinafter, also referred to as aggregation / fusion process).

  Hereinafter, each process (c)-(e) arbitrarily performed other than each process (a) and (b) and these processes is explained in full detail.

(A) Preparation Step The step (a) includes the following preparation steps of the hybrid crystalline polyester resin fine particle dispersion and the non-crystalline resin fine particle dispersion, and, if necessary, the colorant dispersion preparation step or A template fine particle dispersion liquid preparation process etc. are included.

(A-1) Hybrid Crystalline Polyester Resin Fine Particle Dispersion Preparation Step The hybrid crystalline polyester resin (hybrid resin) fine particle dispersion preparation step synthesizes a hybrid resin constituting toner particles, and this hybrid resin is contained in an aqueous medium. This is a step of dispersing in the form of fine particles to prepare a dispersion liquid of hybrid resin fine particles.

  Since the method for producing the hybrid resin is as described above, details are omitted, but in order to satisfy the above formulas (1) and (2), the crystalline polyester resin unit and the amorphous resin unit in the hybrid resin It is preferable to make a content rate into the said preferable range. In addition, types (chemical structures) of hybrid resin and amorphous resin, in particular, carbon number (C (alcohol)) and polyhydric carboxylic acid component of polyhydric alcohol component constituting the crystalline polyester resin unit in the hybrid resin The carbon number (C (acid)) or the like may be adjusted to make the above-mentioned preferable range.

  The hybrid resin fine particle dispersion is, for example, a method of performing dispersion treatment in an aqueous medium without using a solvent, or a hybrid resin is dissolved in a solvent such as ethyl acetate to form a solution, and the solution is used as an aqueous medium using a disperser. After emulsifying and dispersing in the solution, a method of solvent removal treatment may, for example, be mentioned.

  In the present invention, the "aqueous medium" refers to one containing at least 50% by mass of water, and examples of components other than water include organic solvents soluble in water, such as methanol, ethanol and isopropanol Butanol, acetone, methyl ethyl ketone, dimethylformamide, methyl cellosolve, tetrahydrofuran and the like. Among these, it is preferable to use an alcohol-based organic solvent such as methanol, ethanol, isopropanol or butanol, which is an organic solvent which does not dissolve the resin. Preferably, only water is used as the aqueous medium.

  The hybrid resin may contain a carboxyl group in the crystalline polyester resin unit. In such a case, it is possible to add ammonia, sodium hydroxide or the like in order to cause ion dissociation of the carboxyl group contained in the unit and stably emulsify in the aqueous phase to smoothly emulsify.

  Furthermore, in the aqueous medium, a dispersion stabilizer may be dissolved, and a surfactant, fine resin particles and the like may be added for the purpose of improving the dispersion stability of oil droplets.

  As the dispersion stabilizer, known ones can be used. For example, it is preferable to use ones which are soluble in acid or alkali such as tricalcium phosphate or the like, or from the viewpoint of environment, by enzymes It is preferable to use a degradable one.

  As the surfactant, known anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used.

  Moreover, as resin fine particles for the improvement of dispersion stability, polymethyl methacrylate resin fine particles, polystyrene resin fine particles, polystyrene-acrylonitrile resin fine particles, etc. may be mentioned.

  Such dispersion processing can be carried out using mechanical energy, and the dispersion machine is not particularly limited, and a homogenizer, a low speed shear type disperser, a high speed shear type disperser, a friction type dispersion, etc. Machines, high pressure jet type dispersers, ultrasonic dispersers, high pressure impact type disperser Ultimizer and the like.

  The particle diameter of the hybrid resin fine particles (oil droplets) in the hybrid resin fine particle dispersion prepared in this manner is preferably 60 to 1000 nm, and more preferably 80 to 500 nm, as a volume-based median diameter. In addition, this volume average particle diameter is measured by the method as described in an Example. The volume average particle size of the oil droplets can be controlled by the magnitude of mechanical energy at the time of emulsification and dispersion.

  Further, the content of the hybrid resin fine particles in the hybrid resin fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass with respect to 100% by mass of the dispersion. Within such a range, the spread of the particle size distribution can be suppressed, and the toner characteristics can be improved.

(A-2) Amorphous Resin Fine Particle Dispersion Preparation Step In the amorphous resin fine particle dispersion preparation step, an amorphous resin constituting toner particles is synthesized, and this amorphous resin is made into fine particles in an aqueous medium. The dispersion is carried out to prepare a dispersion liquid of amorphous resin fine particles.

  Since the method of producing the amorphous resin is as described above, the details will be omitted.

  As a method of dispersing an amorphous resin in an aqueous medium, a method of forming amorphous resin fine particles from monomers for obtaining an amorphous resin, and preparing an aqueous dispersion of the amorphous resin fine particles (I) or an amorphous resin is dissolved or dispersed in an organic solvent (solvent) to prepare an oil phase liquid, and the oil phase liquid is dispersed in an aqueous medium by phase inversion emulsification or the like to obtain desired particles. After forming an oil droplet in a state where the diameter is controlled, a method (II) of removing the organic solvent (solvent) and the like can be mentioned.

  In method (I), first, monomers for obtaining an amorphous resin are added to an aqueous medium together with a polymerization initiator and polymerized to obtain basic particles. Next, a radically polymerizable monomer and a polymerization initiator for obtaining the amorphous resin are added to the dispersion in which the resin fine particles are dispersed, and the radically polymerizable monomer is seeded to the above base particles. It is preferable to use a polymerization method.

  At this time, a water-soluble polymerization initiator can be used as the polymerization initiator. As the water-soluble polymerization initiator, for example, water-soluble radical polymerization initiators such as potassium persulfate and ammonium persulfate can be suitably used.

  In addition, a chain transfer agent generally used can be used in the seed polymerization reaction system for obtaining amorphous resin fine particles for the purpose of adjusting the molecular weight of the amorphous resin. As chain transfer agents, mercaptans such as octyl mercaptan, dodecyl mercaptan and t-dodecyl mercaptan; mercaptopropionic acids such as n-octyl 3-mercaptopropionate and stearyl 3-mercaptopropionate; and styrene dimer It can be used. These can be used singly or in combination of two or more.

  In the method (I), when forming the amorphous resin fine particles from the monomer for obtaining the amorphous resin, the mold release agent is dispersed together with the above-mentioned monomer to release the resin in the core part. An agent may be contained.

  In the method (II), as the organic solvent (solvent) used for the preparation of the oil phase liquid, the boiling point is low and water is also similar to the above, from the viewpoint of easy removal treatment after formation of oil droplets. Those having low solubility in water are preferable, and specific examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl isobutyl ketone, toluene, xylene and the like. These can be used singly or in combination of two or more.

  The amount of the organic solvent (solvent) used (the total amount used when two or more are used) is usually 10 to 500 parts by mass, preferably 100 to 450 parts by mass, further 100 parts by mass of the amorphous resin Preferably it is 200-400 mass parts.

  The use amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid. By setting the amount of the aqueous medium to be in the above range, the oil phase liquid can be emulsified and dispersed to a desired particle size in the aqueous medium.

  Further, as in the above, in the aqueous medium, the dispersion stabilizer may be dissolved, and even if a surfactant or resin fine particles are added for the purpose of improving the dispersion stability of the oil droplets. Good.

  Emulsify and dispersion of such an oil phase liquid can be performed using mechanical energy in the same manner as described above, and a disperser for performing emulsification and dispersion is not particularly limited, and the above-mentioned (a The one described in -1) can be used.

  The removal of the organic solvent after the formation of the oil droplets is carried out by gradually raising the temperature of the whole dispersion in a state where the amorphous resin fine particles are dispersed in the aqueous medium under stirring, giving strong stirring in a certain temperature range. After that, the solvent can be removed by an operation such as desolvation. Alternatively, it can be removed while reducing pressure using an apparatus such as an evaporator.

  The particle diameter of the non-crystalline resin fine particles (oil droplets) in the non-crystalline resin fine particle dispersion prepared by the above method (I) or (II) is 60 to 1000 nm as a volume-based median diameter Preferably, it is 80 to 500 nm. In addition, this volume average particle diameter is measured by the method as described in an Example. The volume average particle size of the oil droplets can be controlled by the magnitude of mechanical energy at the time of emulsification and dispersion.

  The content of the non-crystalline resin particles in the non-crystalline resin particle dispersion is preferably in the range of 5 to 50% by mass, and more preferably in the range of 10 to 30% by mass. Within such a range, the spread of the particle size distribution can be suppressed, and the toner characteristics can be improved.

(A-3) Colorant Dispersion Preparation Step / Release Agent Fine Particle Dispersion Preparation Step In the colorant dispersion preparation step, a colorant is dispersed in the form of fine particles in an aqueous medium to prepare a dispersion of colorant fine particles. It is a process. Further, the releasing agent fine particle dispersion preparing step is a step which is carried out as necessary when toner particles containing a releasing agent are desired, and the releasing agent is dispersed in the form of fine particles in an aqueous medium. This is a step of preparing a dispersion of release agent fine particles.

  The said aqueous medium is as having demonstrated by said (a-1), In this aqueous medium, surfactant, resin fine particle, etc. may be added in order to improve dispersion stability.

  Dispersion of the coloring agent / releasing agent can be carried out by utilizing mechanical energy, and such a dispersing machine is not particularly limited, and one described in the above (a-1) is used. be able to.

  The content of the colorant in the colorant dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, there is an effect of securing color reproducibility. The content of the release agent particles in the release agent particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, the effect of preventing hot offset and securing separability can be obtained.

(B) Coagulation and Fusion Step In this aggregation and fusion step, the above-mentioned hybrid resin fine particles and amorphous resin fine particles and, if necessary, colorant particles and / or release agent fine particles are agglomerated in an aqueous medium And coagulating these particles at the same time to obtain a binder resin.

  In this step, the dispersion is mixed so as to satisfy the above formulas (1) and (2). Here, in order to satisfy the above formulas (1) and (2), the content ratio of the hybrid resin and the non-crystalline resin in the binder resin is adjusted, and the amount of each dispersion is adjusted so as to fall within the above preferable range. Then, it is suitable.

  In this step, first, hybrid resin fine particles and non-crystalline resin fine particles and, if necessary, colorant particles and / or release agent so that a binder resin satisfying the above formulas (1) and (2) is obtained. The particles are mixed with the particles, and the particles are dispersed in an aqueous medium. Next, after adding an alkali metal salt or a salt containing a Group 2 element as a coagulant, the mixture is heated at a temperature higher than the glass transition temperature of the hybrid resin fine particles and the non-crystalline resin fine particles to promote aggregation, and simultaneously the resin The particles are fused together.

  Specifically, the dispersion of the hybrid resin and the dispersion of the amorphous resin prepared according to the above-mentioned procedure are mixed with the colorant particle dispersion and / or the release agent fine particle dispersion, if necessary, By adding an aggregating agent such as magnesium chloride, the hybrid resin fine particles and the non-crystalline resin fine particles, and if necessary, the colorant particles and / or the release agent fine particles are coagulated, and at the same time, the particles fuse together. A binder resin is formed. Then, when the size of the aggregated particles reaches a target size, a salt such as saline is added to stop aggregation.

  The aggregating agent used in this step is not particularly limited, but those selected from metal salts are suitably used. For example, salts of monovalent metals such as salts of alkali metals such as sodium, potassium and lithium, salts of divalent metals such as calcium, magnesium, manganese and copper, trivalent metals such as iron and aluminum There is salt etc. Specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate and the like, and among them, divalent metals are particularly preferable. It is salt. Aggregation can be promoted with smaller amounts by using salts of divalent metals. These flocculants can be used alone or in combination of two or more.

  In the aggregation step, it is preferable to minimize the standing time (time to start heating) to be left after addition of the coagulant as much as possible. That is, after the coagulant is added, it is preferable to start heating the dispersion liquid for aggregation as quickly as possible and to bring it to a temperature equal to or higher than the glass transition temperature of the hybrid resin and the amorphous resin. The reason for this is not clear, but the aggregation state of the particles may change with the lapse of the standing time, and the particle size distribution of the obtained toner particles may become unstable or the surface properties may fluctuate. It is because there is. The standing time is usually within 30 minutes, preferably within 10 minutes. The temperature at which the coagulant is added is not particularly limited, but is preferably equal to or less than the glass transition temperature of the hybrid resin as the binder resin and the amorphous resin.

  In addition, in the aggregation step, it is preferable to rapidly raise the temperature by heating after adding the coagulant, and the temperature rising rate is preferably 0.8 ° C./min or more. The upper limit of the temperature raising rate is not particularly limited, but is preferably 15 ° C./min or less from the viewpoint of suppressing the generation of coarse particles due to the progress of rapid fusion. Furthermore, after the aggregation dispersion liquid reaches a temperature above the glass transition temperature, the temperature of the aggregation dispersion liquid is maintained for a certain period of time, preferably until the median diameter on a volume basis becomes 4.5 to 7.0 μm. Therefore, it is important to continue the fusion (the first aging step). In addition, it is preferable to measure the average circularity of the particles during ripening, and to carry out the first ripening step until preferably 0.92 to 1.000.

  By this, the growth of particles (hybrid resin fine particles, amorphous resin fine particles, and, if necessary, aggregation of colorant particles / releasing agent fine particles) and fusion (disappearance of the interface between particles) are effectively made. It is possible to improve the durability of the finally obtained toner particles.

  When a binder resin having a core-shell structure is to be obtained, an aqueous dispersion of a resin (preferably, the above amorphous resin) forming the shell portion is further added in the above-mentioned first ripening step, The resin forming the shell portion is coagulated and fused on the surface of the binder resin particle (core particle) of the single layer structure obtained above. Thereby, a binder resin having a core-shell structure is obtained (shelling process). At this time, following the shelling step, it is preferable to further heat-process the reaction system until the aggregation and fusion of the shell on the core particle surface are strengthened and the particle shape becomes a desired shape (second Maturation process). The second ripening step may be performed until the average circularity of the toner particles having a core-shell structure falls within the above-mentioned range of the average circularity.

(C) Cooling Step The cooling step is a step of cooling the dispersion of toner particles. The cooling rate in the cooling treatment is not particularly limited, but is preferably 0.2 to 20 ° C./min. It does not specifically limit as a cooling processing method, The method of introduce | transducing and cooling a refrigerant | coolant from the exterior of a reaction container, and the method of injecting | throwing-in cold water directly to a reaction system and cooling can be illustrated.

(D) Filtration, Washing, Drying Step In the filtration step, toner particles are separated from the dispersion of toner particles. The filtration method includes, but is not particularly limited to, a centrifugal separation method, a vacuum filtration method performed using Nutsche, a filtration method performed using a filter press, and the like.

  Next, from the toner particles (cake-like aggregate) separated by filtration by washing in the washing step, deposits such as surfactants and coagulants are removed. In the washing process, the water washing process is performed until the electric conductivity of the filtrate becomes, for example, 5 to 10 μS / cm level.

  In the drying step, the washed toner particles are subjected to a drying treatment. Examples of the dryer used in this drying step include known dryers such as a spray dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a movable shelf dryer, a fluidized bed dryer, a rotary dryer, and the like. It is also possible to use a drier, a stirring drier or the like. The amount of water contained in the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

  Further, when the dried toner particles are aggregated due to weak interparticle attraction, crushing may be performed. As a crushing processing apparatus, mechanical crushing apparatuses, such as a jet mill, a Henschel mixer, a coffee mill, and a food processor, can be used.

(E) External Additive Treatment Step This step is a step of adding an external additive to the surface of the dried toner particles, if necessary, and mixing to prepare a toner. By the addition of the external additive, the flowability and chargeability of the toner are improved, and the improvement of the cleaning property is realized.

(Developer)
For example, when the toner as described above contains a magnetic substance and is used as a one-component magnetic toner, when it is mixed with a so-called carrier and used as a two-component developer, it is considered that the non-magnetic toner is used alone. And any of them can be suitably used.

  As carriers constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of such metals with metals such as aluminum and lead can be used, and in particular It is preferable to use ferrite particles.

  The carrier preferably has a volume average particle diameter of 15 to 100 μm, and more preferably 25 to 60 μm.

  As the carrier, it is preferable to use one further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and, for example, an olefin resin, a cyclohexyl methacrylate-methyl methacrylate copolymer, a styrene resin, a styrene acrylic resin, a silicone resin, an ester resin or a fluorine resin is used. The resin for forming the resin dispersion type carrier is not particularly limited, and any known resin can be used. For example, acrylic resin, styrene acrylic resin, polyester resin, fluorocarbon resin, phenol resin, etc. may be used. Can.

<Fixing method>
As a suitable fixing method using the toner of the present invention, a so-called contact heating method can be mentioned. As the contact heating method, particularly, a heat pressure fixing method, a heat roll fixing method, and a pressure contact heating fixing method of fixing by a rotating pressing member including a fixedly arranged heating body can be mentioned.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to said aspect, A various change can be added.

  Hereinafter, representative embodiments of the present invention will be shown and the present invention will be further described, but of course, the present invention is not limited to these embodiments. In the examples, unless otherwise noted, "part" represents "part by mass", and "%" represents "% by mass".

<Measurement method>
(Endothermic peak temperature (Tm1) derived from the hybrid crystalline polyester resin, endothermic amount (ΔH1, ΔH2))
The endothermic peak temperature (Tm1) and the endothermic amount (ΔH1, ΔH2) were determined by performing differential scanning calorimetry of the toner. For differential scanning calorimetry, a differential scanning calorimeter "diamond DSC" (manufactured by Perkin Elmer) was used. The measurement is performed by raising the temperature from room temperature (25 ° C.) to 150 ° C. at a lifting rate of 10 ° C./min and holding isothermally at 150 ° C. for 5 minutes. The measurement conditions are as follows: a cooling process that cools to 0 ° C and isothermal holding at 0 ° C for 5 minutes, and a second heating process that raises the temperature from 0 ° C to 150 ° C at a lifting speed of 10 ° C / min. The condition was done. The above measurement was performed by enclosing 3.0 mg of toner in an aluminum pan and setting it in a sample holder of a differential scanning calorimeter “diamond DSC”. An empty aluminum pan was used as a reference.

  In the above measurement, the heat absorption amount based on the melting peak derived from the hybrid crystalline polyester resin in the first heating process (endothermic peak whose half width is within 15 ° C.) is ΔH1 (J / g), the second heating The heat absorption amount based on the melting peak derived from the hybrid crystalline polyester resin in the process was taken as ΔH 2 (J / g). In the above measurement, analysis is performed from the endothermic curve obtained in the first temperature raising process, and the top temperature of the endothermic peak derived from the hybrid crystalline polyester resin (endothermic peak whose half width is within 15 ° C.) is Tm1 (° C.).

(Melting point (Tc) and glass transition temperature (Tg) of each resin)
The melting point and the glass transition temperature of each resin constituting the toner were determined by performing differential scanning calorimetry on each resin. The same differential scanning calorimetry as described above was used. The measurement was carried out in the same manner as the above measurement conditions (temperature rise and cooling conditions). The above measurement was carried out by sealing 3.0 mg of each resin in an aluminum pan and setting it in a sample holder of a differential scanning calorimeter "diamond DSC". An empty aluminum pan was used as a reference.

  In the above measurement, the top temperature of the melting peak of the resin (the endothermic peak whose half width is within 15 ° C.) in the first temperature raising process is taken as the melting point (Tc) of the resin. In addition, for the amorphous resin, in the above measurement, the onset temperature obtained from the endothermic curve obtained by the first heating process was obtained by the glass transition temperature Tg1 (° C.) and the second heating process. The onset temperature was taken as the glass transition temperature Tg2 (° C.).

(Measurement of weight average molecular weight (Mw))
The weight-average molecular weight (Mw) (in terms of polystyrene) of each resin is “HLC-8220” (manufactured by Tosoh Corp.) as a GPC apparatus and “TSKguard column + TSKgelSuperHZM-M3 series” (manufactured by Tosoh Corp.) as a column, and the column temperature is 40 While maintaining the temperature in ° C, pour tetrahydrofuran (THF) as a carrier solvent at a flow rate of 0.2 ml / min, and use a ultrasonic dispersion machine to treat the measurement sample for 5 minutes at room temperature to a concentration of 1 mg / ml The sample solution is dissolved in tetrahydrofuran and then treated with a membrane filter with a pore size of 0.2 μm to obtain a sample solution, 10 μL of this sample solution is injected into the apparatus together with the above carrier solvent, and a refractive index detector (RI detector) Use the monodisperse molecular weight distribution of the measurement sample to detect Calculate using the calibration curve measured using polystyrene standard particles. As a standard polystyrene sample for standard curve measurement, the molecular weight by Pressure Chemical company is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1 Measure at least 10 standard polystyrene samples using 1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ samples, and use a calibration curve It was created. Moreover, the refractive index detector was used for the detector.

(Average particle size of resin particles, colorant particles, etc.)
The volume average particle diameter (median diameter on a volume basis) of resin particles, colorant particles and the like was measured by "UPA-150" (manufactured by Microtrac).

(Observation by TEM)
The fine structure of the binder resin constituting the toner particles was carried out as follows using a transmission electron microscope (TEM).

  First, toner particles are sufficiently dispersed in a room temperature curing epoxy resin, embedded, embedded in a fine styrene powder having a particle diameter of about 100 nm, and then subjected to pressure molding to contain the toner. Was produced. Subsequently, the block produced was subjected to a staining process using osmium tetraoxide if necessary, and then cut into a thin plate having a thickness of 80 to 200 nm with a microtome equipped with a diamond tooth to prepare a measurement sample.

  Next, the flaky measurement sample was set on a transmission electron microscope (TEM) to photograph the cross-sectional structure of the toner. The magnification of the electron microscope was 5,000 times.

<Production of Toner Particles>
Production Example 1: Preparation of Releasing Agent Particle Dispersion (W)
60 parts by mass of behenyl behenate (melting point 73 ° C.) as a release agent, 5 parts by mass of an ionic surfactant “NEOGEN RK” (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and 240 parts by mass of ion exchanged water The resulting solution is heated to 95.degree. C., sufficiently dispersed using a homogenizer "Ultratax T50" (manufactured by IKA Co., Ltd.), and then dispersed using a pressure discharge type Gaulin homogenizer to obtain a solid content of 20% by mass A release agent particle dispersion (W) was prepared. The volume average particle diameter of the particles in the release agent particle dispersion was 240 nm.

Synthesis Example 1: Synthesis of Hybrid Crystalline Polyester Resin (c1)
Raw material monomers of the following addition polymerization resin (styrene acrylic resin: StAc) unit and a radical polymerization initiator containing both reactive monomers were placed in the dropping funnel.

Styrene 34 parts by mass n-butyl acrylate 12 parts by mass Acrylic acid 2 parts by mass Polymerization initiator (di-t-butyl peroxide) 7 parts by mass.

  In addition, the raw material monomers of the following polycondensation resin (crystalline polyester resin: CPEs) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to 170 ° C and dissolved. I did.

Sebacic acid 275 parts by mass 1,12-dodecanediol 277 parts by mass.

  Next, under stirring, the raw material monomer of the addition polymerization resin (StAc) was dropped over 90 minutes, and after aging for 60 minutes, the unreacted addition polymerization monomer was removed under reduced pressure (8 kPa). The amount of monomer removed at this time was very small relative to the raw material monomer ratio of the above resin.

Then, 0.8 parts by mass of Ti (OBu) ₄ as an esterification catalyst is added, the temperature is raised to 235 ° C., and the reaction is conducted for 5 hours under normal pressure (101.3 kPa) and further for 1 hour under reduced pressure (8 kPa). went.

  Next, after cooling to 200 ° C., a hybrid crystalline polyester resin (c1) was obtained by reacting under reduced pressure (20 kPa) for 1 hour. The hybrid crystalline polyester resin (c1) contained 8% by mass of a resin (StAc) unit other than CPEs with respect to the total amount, and was a resin in a form in which CPEs was grafted to StAc. The weight average molecular weight (Mw) of the hybrid crystalline polyester resin (c1) was 14,000, and the melting point (Tc) was 76 ° C.

Synthesis Examples 2 to 5: Synthesis of Hybrid Crystalline Polyester Resins (c2) to (c5)
Except that the addition amount of the raw material monomer of the polycondensation resin (CPEs) is changed such that the content ratio of the addition polymerization resin (StAc) unit in the hybrid crystalline polyester resin becomes the value of Table 1-1, Hybrid crystalline polyester resins (c2) to (c5) were obtained in the same manner as in Synthesis Example 1. At this time, the composition ratio of the raw material monomer of the addition polymerization resin (StAc), the addition amount of the raw material monomer, and the composition ratio of the raw material monomer of the polycondensation resin (CPEs) were the same as those in Synthesis Example 1 above. The weight average molecular weights (Mw) of the hybrid crystalline polyester resins (c2) to (c5) are shown in Table 1-1, respectively.

Synthesis Examples 6 to 12 Synthesis of Hybrid Crystalline Polyester Resins (c6) to (c12)
Hybrid crystalline polyester resins (c6) to (c12) were prepared in the same manner as in Synthesis Example 1 except that the types and addition amounts of the raw material monomers of the polycondensation resin (CPEs) unit were changed as follows. Obtained. At this time, the composition ratio of the raw material monomer of the addition polymerization resin (StAc) and the addition amount of the raw material monomer were the same as in the above-mentioned Synthesis Example 1. The weight average molecular weights (Mw) of the hybrid crystalline polyester resins (c6) to (c12) are shown in Table 1-1, respectively.

«Hybrid crystalline polyester resin (c6)»
Adipic acid 255 parts by mass 1, 297 parts by mass of 1,4-butanediol.

«Hybrid crystalline polyester resin (c7)»
Dodecanedioic acid 410 parts by mass Ethylene glycol 142 parts by mass.

«Hybrid crystalline polyester resin (c8)»
292 parts by mass of dodecanedioic acid 260 parts by mass of 1,9-nonanediol.

«Hybrid crystalline polyester resin (c9)»
Adipic acid 200 parts by mass 1,12-dodecanediol 352 parts by mass.

«Hybrid crystalline polyester resin (c10)»
Adipic acid 358 parts by mass Ethylene glycol 194 parts by mass.

«Hybrid crystalline polyester resin (c11)»
Dodecanedioic acid 411 parts by mass Ethylene glycol 141 parts by mass.

«Hybrid crystalline polyester resin (c12)»
Adipic acid 66 parts by mass 1, 4-butanediol 76 parts by mass.

Synthesis Example 13 Synthesis of Hybrid Crystalline Polyester Resin (c13)
The raw material monomers of the following polycondensation resin (crystalline polyester resin: CPEs) unit containing both reactive monomers are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, 170 The mixture was heated to 0 C and dissolved.

Sebacic acid 275 parts by mass 1,12-dodecanediol 277 parts by mass Methylene succinic acid 23 parts by mass.

Then, 0.8 parts by mass of Ti (OBu) ₄ as an esterification catalyst is added, the temperature is raised to 235 ° C., and the reaction is conducted for 5 hours under normal pressure (101.3 kPa) and further for 1 hour under reduced pressure (8 kPa). went.

  Subsequently, the raw material monomer and radical polymerization initiator of the following addition polymerization type-resin (styrene acrylic resin: StAc) unit were put into the dropping funnel.

Styrene 37 parts by weight n-butyl acrylate 13 parts by weight Polymerization initiator (di-t-butyl peroxide) 7 parts by weight.
Next, under stirring, the raw material monomer of the addition polymerization resin (StAc) was dropped over 90 minutes, and after aging for 60 minutes, the unreacted addition polymerization monomer was removed under reduced pressure (8 kPa). The amount of monomer removed at this time was very small relative to the raw material monomer ratio of the above resin.

  Next, after cooling to 170 ° C., a hybrid crystal having a graft structure having a crystalline polyester resin unit (CPEs) as a trunk and a vinyl resin unit (StAc) as a branch by reacting under reduced pressure (20 kPa) for 1 hour Crystalline polyester resin (c13) was synthesized. The weight average molecular weight (Mw) of the hybrid crystalline polyester resin (c13) was 1,5,000, and the melting point (Tc) was 76 ° C.

Synthesis Example 14 Synthesis of Hybrid Crystalline Polyester Resin (c14)
Raw material monomers of the following addition polymerization resin (styrene acrylic resin: StAc) unit and a radical polymerization initiator containing both reactive monomers were placed in the dropping funnel.

Styrene 34 parts by mass n-butyl acrylate 12 parts by mass Acrylic acid 2 parts by mass Polymerization initiator (di-t-butyl peroxide) 7 parts by mass.

  Next, under stirring, the raw material monomer of the addition polymerization resin (StAc) is dropped over 90 minutes, and after aging for 60 minutes, the unreacted addition polymerization monomer is removed under reduced pressure (8 kPa), and the vinyl resin is removed. I got (1). The amount of monomer removed at this time was very small relative to the raw material monomer ratio of the above resin.

Next, 281 parts by mass of sebacic acid and 283 parts by mass of dodecanediol were placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introduction pipe. After replacing the inside of the reaction vessel with dry nitrogen gas, 0.1 parts by mass of Ti (OBu) ₄ was added, and stirring reaction was performed at about 180 ° C. for 8 hours under nitrogen gas flow. Further, 0.2 parts by mass of Ti (OBu) ₄ is added, the temperature is raised to about 220 ° C., and stirring reaction is carried out for 6 hours, the pressure in the reaction vessel is reduced to 10 mmHg, and the reaction is carried out under reduced pressure I got (1). The weight average molecular weight (Mw) of the crystalline polyester resin (1) was 13,000.

  The vinyl resin (1) and the crystalline polyester resin (1) obtained above were block copolymerized in the following procedure.

  First, 92 parts by mass of the crystalline polyester resin (1) and 8 parts by mass of the vinyl resin (1) are charged into a glass container equipped with a reflux condenser, a nitrogen introducing pipe and a stirrer, and dissolved by stirring at 50 ° C. It is a block copolymer of a vinyl resin and a crystalline polyester resin by adding 2.7 parts of dicyclocarbodiimide (DCC) and 0.17 parts of dimethylaminopyridine (DMAP) and reacting for 2 hours at 50 ° C. , And a hybrid crystalline polyester resin (c14). The weight average molecular weight (Mw) of the hybrid crystalline polyester resin (c14) was 29,000, and the melting point (Tc) was 76 ° C.

Preparation Example 2 Preparation of Aqueous Dispersion (C1) of Hybrid Crystalline Polyester Resin Fine Particles
200 parts by mass of the hybrid crystalline polyester resin (c1) obtained in the above Synthesis Example 1 is dissolved in 200 parts by mass of ethyl acetate, and while stirring this solution, sodium polyoxyethylene lauryl ether sulfate is added to 800 parts by mass of ion exchanged water An aqueous solution in which the concentration was 1% by mass was slowly dropped. After removing ethyl acetate under reduced pressure, this solution was adjusted to pH 8.5 with ammonia. Thereafter, the solid content concentration was adjusted to 30% by mass. Thus, an aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles in which the fine particles of the hybrid crystalline polyester resin (c1) were dispersed in the aqueous medium was prepared. At this time, the particles contained in the dispersion liquid (C1) had a volume-based median diameter of 205 nm.

Production Examples 3 to 15 Preparation of Aqueous Dispersions (C2) to (C14) of Hybrid Crystalline Polyester Resin Fine Particles
An aqueous dispersion of fine particles of hybrid crystalline polyester resin (the same as in Production Example 2) except that hybrid crystalline polyester resins (c2) to (c14) were used instead of hybrid crystalline polyester resin (c1) C2) to (C14) were prepared respectively. At this time, the particles contained in the dispersions (C2) to (C14) had a volume-based median diameter in the range of 180 to 240 nm.

Preparation Example 16 Preparation of Aqueous Dispersion (C15) of Seeded Crystalline Polyester Resin Fine Particles
220 parts by mass of sebacic acid and 157 parts by mass of 1,4-butanediol are charged into a 5 L reaction vessel equipped with a stirrer, temperature sensor, condenser and nitrogen introduction device, and the system is stirred for 1 hour while stirring The temperature was raised to 190 ° C. After confirming that the state was uniformly stirred, Ti (OBu) ₄ as a catalyst was added in an amount of 0.003% by mass with respect to the preparation amount of sebacic acid. Thereafter, while distilling off the water to be produced, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours, and the polymerization is carried out by continuing the dehydration condensation reaction for 6 hours under the conditions of 240 ° C. Thus, a crystalline polyester resin (2) was obtained.

  200 parts by mass of the crystalline polyester resin (2) is dissolved in 200 parts by mass of ethyl acetate, and while stirring this solution, the concentration of sodium polyoxyethylene lauryl ether sulfate is 1% by mass in 800 parts by mass of ion exchanged water The dissolved aqueous solution was slowly dropped. After removing ethyl acetate under reduced pressure, this solution was adjusted to pH 8.5 with ammonia. Thereafter, the solid content concentration was adjusted to 30% by mass. Thus, a fine particle dispersion of crystalline polyester resin (2) in which fine particles of crystalline polyester resin (2) were dispersed in an aqueous medium was prepared. At this time, the particles contained in the dispersion had a volume-based median diameter of 200 nm.

  Then, 145 parts by mass of the fine particle dispersion of the crystalline polyester resin (2) was added to a 0.5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introduction device, W) 65 parts by mass and 125 parts by mass of ion exchanged water were charged, and further, a polymerization initiator solution in which 1.0 part by mass of potassium persulfate was dissolved in 21 parts by mass of ion exchanged water was added. It consists of a radically polymerizable monomer unit consisting of 32 parts by mass of styrene, 9.4 parts by mass of n-butyl acrylate and 2.2 parts by mass of methacrylic acid under an temperature condition of 80 ° C. and 0.8 parts by mass of n-octyl mercaptan After the polymerizable monomer mixture was dropped over 2 hours, seed polymerization was performed by heating and stirring at 80 ° C. for 2 hours. After the polymerization is completed, the system is cooled to 28 ° C., whereby an aqueous system of binder resin fine particles having a core-shell structure in which an amorphous resin is coated on a core particle composed of a crystalline polyester resin (2). A dispersion (hereinafter, also referred to as an aqueous dispersion (C15) of seeded crystalline polyester resin fine particles) was prepared. At this time, the particles contained in the dispersion liquid (C15) had a volume-based median diameter of 220 nm. Moreover, the weight average molecular weight (Mw) was 19,500.

Preparation Example 17 Preparation of Aqueous Dispersion (C16) of Crystalline Polyester Resin Fine Particles
An aqueous dispersion of a crystalline polyester resin was carried out in the same manner as in Production Example 2 except that the crystalline polyester resin (1) obtained in the above Synthesis Example 14 was used instead of the hybrid crystalline polyester resin (c1). A solution (C16) was prepared. At this time, the particles contained in the dispersion liquid (C16) had a volume-based median diameter of 190 nm.

Preparation Example 18 Preparation of Aqueous Dispersion (A1) of Amorphous Resin Fine Particles
«First Stage Polymerization»
8 parts by mass of sodium dodecyl sulfate and 3000 parts by mass of ion-exchanged water are charged into a 5 L reaction vessel equipped with an agitator, temperature sensor, cooling pipe, and nitrogen introducing device, and are stirred at a stirring speed of 230 rpm under nitrogen stream. The temperature was raised to 80 ° C. After the temperature rise, 10 parts by mass of potassium persulfate dissolved in 200 parts by mass of ion exchanged water is added, and the liquid temperature is again adjusted to 80 ° C.,
Styrene 480 parts by mass n-butyl acrylate 250 parts by mass Methacrylic acid 68.0 parts by mass A monomer mixture consisting of 68.0 parts by mass is added dropwise over 1 hour, and then polymerization is carried out by heating and stirring at 80 ° C. for 2 hours. A dispersion of fine particles (x1) was prepared.

«Second step polymerization»
A solution of 7 parts by mass of sodium polyoxyethylene (2) dodecyl ether sulfate in 3000 parts by mass of ion-exchanged water is charged into a 5-liter reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device. After heating to ° C., 260 parts by mass of dispersion liquid of resin fine particles (x1),
Styrene (St) 284 parts by mass n-butyl acrylate (BA) 92 parts by mass Methacrylic acid (MAA) 13 parts by mass n-octyl-3-mercaptopropionate 1.5 parts by mass Releasing agent: behenyl behenate (melting point) 73 ° C.) A solution of 190 parts by mass of a monomer and a releasing agent dissolved at 90 ° C. is added, and a mechanical disperser “CLEARMIX” (manufactured by M. Technics Co., Ltd.) having a circulation path is used. The mixture was time-mixed and dispersed to prepare a dispersion containing emulsified particles (oil droplets).

  Then, an initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion exchanged water is added to the dispersion, and the system is heated and stirred at 84 ° C. for 1 hour to carry out polymerization A dispersion (x2) of resin fine particles was prepared.

«Third step polymerization»
Furthermore, 400 parts by mass of ion exchange water is added to the dispersion (x2) of resin fine particles, and after thorough mixing, a solution of 11 parts by mass of potassium persulfate dissolved in 400 parts by mass of ion exchange water is added. Under the temperature conditions of
Styrene (St) 350 parts by mass n-butyl acrylate (BA) 215 parts by mass Acrylic acid (AA) 30 parts by mass n-octyl-3-mercaptopropionate 8 parts by mass of a monomer mixed solution over 1 hour It dripped. After completion of the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, and then cooled to 28 ° C. to prepare an aqueous dispersion (X1) of amorphous resin fine particles composed of a vinyl resin.

  With respect to the aqueous dispersion (X1) of the obtained amorphous resin fine particles, the volume-based median diameter of the amorphous resin fine particles is 220 nm, the glass transition temperature (Tg1) is 55 ° C., and the weight average molecular weight (Mw) is 32, It was 000.

Preparation Example 19 Preparation of Aqueous Dispersion (S1) of Amorphous Resin Fine Particles for Shell
Raw material monomers of the following addition polymerization resin (styrene acrylic resin: StAc) unit and a radical polymerization initiator containing both reactive monomers were placed in the dropping funnel.

Styrene 80 parts by mass n-butyl acrylate 20 parts by mass acrylic acid 10 parts by mass Polymerization initiator (di-t-butyl peroxide) 16 parts by mass.

  In addition, the raw material monomers of the following polycondensation resin (amorphous polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, and dissolved by heating to 170 ° C. The

Bisphenol A propylene oxide 2 molar adduct 285.7 parts by mass Terephthalic acid 66.9 parts by mass Fumaric acid 47.4 parts by mass.

Subsequently, the raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and after aging for 60 minutes, the unreacted addition polymerization monomer was removed under reduced pressure (8 kPa).
Thereafter, 0.4 parts by mass of Ti (OBu) ₄ as an esterification catalyst is added, the temperature is raised to 235 ° C., and the reaction is conducted under normal pressure (101.3 kPa) for 5 hours and further under reduced pressure (8 kPa) for 1 hour went.

  After cooling to 200 ° C., the reaction was carried out under reduced pressure (20 kPa) until the desired softening point was reached. Subsequently, the solvent was removed to obtain a shell resin (s1) as an amorphous resin. The glass transition temperature (Tg1) of the obtained resin for shell (s1) was 61 ° C., and the weight average molecular weight (Mw) was 19,000.

  100 parts by mass of the obtained resin for shell (s1) is dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.), and mixed with 638 parts by mass of 0.26 mass% sodium lauryl sulfate solution prepared in advance. After ultrasonic dispersion for 30 minutes with V-LEVEL 300 μA with ultrasonic homogenizer “US-150T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) while stirring, diaphragm vacuum pump “V-700” (warm state at 40 ° C.) Ethyl acetate is completely removed using BUCHI product) while stirring under reduced pressure for 3 hours to prepare an aqueous dispersion (S1) of amorphous resin fine particles for shell having a solid content of 13.5% by mass. did. At this time, the particles contained in the dispersion liquid (S1) had a volume-based median diameter of 160 nm.

Preparation Example 20 Preparation of Aqueous Dispersion (S2) of Amorphous Resin Fine Particles for Shell
600 parts by mass of water was charged into a 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction device, and the internal temperature was raised to 70 ° C. while stirring under a nitrogen flow at a stirring speed of 230 rpm. After that, 119 parts by mass of styrene, 33 parts by mass of n-butyl acrylate, 8 parts by mass of methacrylic acid, 4.5 parts by mass of n-octylmercaptan are added, and 3 parts by mass of a polymerization initiator (potassium persulfate) is ion exchanged water An aqueous solution dissolved in 40 parts by mass was added, and this system was heated and stirred at 70 ° C. for 10 hours to prepare an aqueous dispersion (S2) of non-crystalline resin microparticles for shell.

  At this time, the weight average molecular weight (Mw) of the resin fine particles contained in the dispersion liquid (S1) was 13,200, the number average particle diameter was 221 nm, and the Tg1 was 55.4 ° C.

Preparation Example 21 Preparation of Aqueous Dispersion of Colorant Particles (Cy1)
90 parts by mass of sodium dodecyl sulfate was added to 1600 parts by mass of ion exchange water. While this solution is being stirred, 420 parts by mass of copper phthalocyanine (CI Pigment Blue 15: 3) is gradually added, and then dispersion treatment is carried out using a stirring apparatus "Clairemix" (manufactured by M. Technics Co., Ltd.) Thus, an aqueous dispersion (Cy1) of colorant particles was prepared.

  In the aqueous dispersion (Cy1) of the colorant particles obtained, the volume-based median diameter of the colorant particles was 110 nm.

Example 1 Production of Cyan Toner (1)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, an aqueous dispersion (X1) of amorphous resin fine particles (200 parts by mass (in terms of solid content)) and an aqueous dispersion (C1) of hybrid crystalline polyester resin microparticles (C1) 250 After adding mass part (solid content conversion) and 2000 mass parts of ion exchange water, 5 mol / L sodium hydroxide aqueous solution was added, and pH was adjusted to ten.

  Thereafter, 30 parts by mass (in terms of solid content) of the aqueous dispersion (Cy1) of colorant particles is added, and then an aqueous solution in which 60 parts by mass of magnesium chloride is dissolved in 60 parts by mass of ion exchanged water is stirred at 30.degree. Added over 10 minutes. Then, after standing for 3 minutes, temperature rising was started, this system was heated up to 80 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining 80 ° C. In this state, the particle size of the associated particles is measured by "Coulter Multisizer 3" (manufactured by Beckman Coulter, Inc.), and when the volume-based median diameter reaches 6.0 μm, An aqueous solution in which 190 parts by mass of sodium chloride was dissolved in 760 parts by mass of ion-exchanged water when 50 parts by mass (in terms of solid content) of the aqueous dispersion (S1) was added over 30 minutes and the supernatant of the reaction liquid became transparent. Was added to stop particle growth. Further, the temperature is raised, and heat fusion is carried out by heating and stirring in a state of 90 ° C., thereby promoting fusion of particles, and using a measuring device “FPIA-2100” (manufactured by Sysmex) of average toner circularity (HPF detection) It cooled to 30 degreeC with the cooling rate of 2.5 degrees C / min, when the number of rounds became 4000) average roundness was 0.945.

  Next, the solid-liquid separated and dewatered toner cake is re-dispersed in ion-exchanged water and repeatedly subjected to solid-liquid separation three times, and then dried at 40 ° C. for 24 hours to obtain toner particles (1). The

  0.6 parts by mass of hydrophobic silica (number average primary particle diameter = 12 nm, degree of hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle diameter = 20 nm) based on 100 parts by mass of the obtained toner particles (1) After adding 1.0 part by mass of hydrophobicity degree = 63) and mixing at a rotor peripheral speed of 35 mm / sec at 32 ° C for 20 minutes with a "Henshell mixer" (manufactured by Mitsui Miike Koki Co., Ltd.), 45 μm openings By applying an external additive treatment to remove coarse particles using a sieve, cyan toner (1) having a volume average particle diameter of 6.1 μm was obtained. Tm1, ΔH1 and ΔH2 were measured for the obtained cyan toner (1) as described above. The results are shown in Table 1-2. The Tm1 of the cyan toner (1) by differential scanning calorimetry and the melting point (Tc) of the hybrid crystalline polyester resin (c1) constituting the toner particle (1) are substantially the same, and such a tendency is It was also found in toner particles for the following examples and comparative examples. Further, when the fine structure of the binder resin constituting the toner particles was observed by the above method (observation by TEM), the hybrid crystalline polyester resin constitutes a dispersed phase (domain) and the amorphous resin constitutes a continuous phase (matrix). The sea-island structure was confirmed.

(Examples 2 to 9: Production of cyan toners (2) to (9))
In the same manner as in Example 1, except that hybrid crystalline polyester resins (C2) to (C9) were used instead of the aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles, cyan toners (2) to (2) (9) was manufactured. Tm1, ΔH1 and ΔH2 were measured for the obtained cyan toners (2) to (9) as described above. The results are shown in Table 1-2. Moreover, when the observation as described above was performed, a sea-island structure similar to that of Example 1 was confirmed. Furthermore, the volume average particle diameter of the cyan toners (C2) to (C9) was in the range of 6.0 to 6.5 μm.

Examples 10 to 14: Production of Cyan Toners (10) to (14)
The same as in Example 1 except that the addition amounts of the respective dispersions are changed such that the content ratio of the hybrid crystalline polyester resin, the amorphous resin and the resin for shell in the binder resin is as shown in Table 1-1. Thus, cyan toners (10) to (14) were produced respectively. Tm1, ΔH1 and ΔH2 were measured for the obtained cyan toners (10) to (14) as described above. The results are shown in Table 1-2. Moreover, when the observation as described above was performed, a sea-island structure similar to that of Example 1 was confirmed. Furthermore, the volume average particle diameters of the cyan toners (C10) to (C14) were in the range of 6.0 to 6.5 μm.

(Example 15 and Reference Example 16: Manufacture of cyan toners (15) and (16))
In the same manner as in Example 1, except that the hybrid crystalline polyester resin (C13) or (C14) was used instead of the aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles, cyan toners (15), 16) were each manufactured. With respect to the obtained cyan toners (15) and (16), Tm1, ΔH1 and ΔH2 were measured as described above. The results are shown in Table 1-2. Moreover, when the observation as described above was performed, a sea-island structure similar to that of Example 1 was confirmed. Furthermore, the volume average particle diameters of the cyan toners (C15) to (C16) were 6.2 μm and 6.3 μm, respectively.

Comparative Examples 1 and 2: Production of Cyan Toner (17) and (18)
In the same manner as in Example 1, except that the hybrid crystalline polyester resin (C10) or (C11) was used instead of the aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles, cyan toners (17), 18) were each manufactured. Tm1, ΔH1 and ΔH2 were measured on the obtained cyan toners (17) and (18) as described above. The results are shown in Table 1-2.

Comparative Example 3 Production of Cyan Toner (19)
A hybrid crystalline polyester resin (C12) is used in place of the aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles, and further, in the binder resin, the hybrid crystalline polyester resin, the amorphous resin and the resin for shell A cyan toner (19) was produced in the same manner as in Example 1 except that the addition amount of each dispersion was changed so that the content ratio would be as shown in Table 1-1. For the obtained cyan toner (19), Tm1, ΔH1 and ΔH2 were measured as described above. The results are shown in Table 1-2.

Comparative Example 4 Production of Cyan Toner (20)
400 parts by mass (C15) of the aqueous dispersion (C15) of seeded crystalline polyester resin fine particles in a zebra flask equipped with a stirrer, temperature sensor, condenser and nitrogen introduction device, and 1500 parts by mass of ion-exchanged water Parts and 165 parts by mass of a colorant particle dispersion (Cy1) were charged, the liquid temperature was adjusted to 30 ° C., and then a 25 mass% aqueous sodium hydroxide solution was added to adjust the pH to 10.

  Next, an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate is dissolved in 54.3 parts by mass of ion-exchanged water is added, and then the temperature of the system is raised to 60 ° C. The aggregation reaction of the particles with the colorant particles was initiated.

  After the initiation of the agglutination reaction, sampling is performed periodically, and the volume-based median diameter of colored particles is measured using a particle size distribution measuring apparatus "Coulter Multisizer 3" (manufactured by Beckman Coulter, Inc.), and the volume-based median diameter When the particle size becomes 5.8 μm, 40 parts by mass (solid content) of the aqueous dispersion (S2) of resin fine particles for shell is added, and 2 parts by mass of magnesium chloride · hexahydrate are further added 2 parts by mass of ion exchanged water The aqueous solution dissolved in the above was added over 10 minutes, and a shell was formed on the surface of the colored particles by continuing stirring until the volume-based median diameter was 6.0 .mu.m. It was 0.951 when circularity was measured about the colored particle in which this shell was formed using flow type particle image analyzer "FPIA-2100" (made by Sysmex). Thereafter, the temperature of the system is raised to 65 ° C. and stirring is continued for 4 hours, and when the circularity reaches 0.976 as measured by a flow type particle image analyzer “FPIA-2100” (manufactured by Sysmex) The cyan toner (20) was produced by cooling the reaction to 30 ° C. at 6 ° C./min to stop the reaction. Tm1, ΔH1 and ΔH2 were measured for the obtained cyan toner (20) as described above. The results are shown in Table 1-2.

Comparative Example 5 Production of Cyan Toner (21)
A cyan toner (21) was produced in the same manner as in Example 1, except that the aqueous dispersion (C16) of the crystalline polyester resin was used instead of the aqueous dispersion (C1) of the hybrid crystalline polyester resin fine particles. . For the obtained cyan toner (21), Tm1, ΔH1 and ΔH2 were measured as described above. The results are shown in Table 1-2.

<Preparation of Developer>
To the cyan toners (1) to (21), a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin is added and mixed so that the toner particle concentration is 6% by mass. 1) to (21) were produced respectively.

<Evaluation method>
(Low temperature fixability)
In the copying machine “bizhub PRO C6501” (manufactured by Konica Minolta Co., Ltd.), the above-described developing agent (the fixing device was modified so that the surface temperature of the fixing heat roller can be changed in the range of 100 to 210 ° C. 1) to (21) were loaded respectively. Fixing experiment to fix a solid image of toner adhesion amount 11 mg / 10 cm ² on A4 size plain paper (basis weight 80 g / m ² ) was changed to increase the fixing temperature set from 85 ° C. by 5 ° C. Repeatedly performed up to 130 ° C.

  Next, the printed matter obtained in the fixing experiment at each fixing temperature is folded by a folding machine so as to apply a load to the solid image, a compressed air of 0.35 MPa is blown thereto, and the fold is indicated by the following evaluation criteria 5 The fixing temperature in the fixing experiment with the lowest fixing temperature among the fixing experiments of rank 3 was ranked as the lower limit fixing temperature. The results are shown in Table 1-2.

  As the lower limit fixing temperature is lower, it means that the low temperature fixing property is excellent, and if it is 120 ° C. or less, it is judged as a pass with no problem in practical use.

«Evaluation criteria»
Rank 5: No crease at all Rank 4: Peeling according to part of the fold Rank 3: Fine linear peeling according to the fold Rank 2: Thick linear peeling according to the fold Rank 1: There is a big peeling.

(Image preservation)
Using the above-mentioned evaluation machine loaded with a dedicated finisher “FS-608” (manufactured by Konica Minolta Business Technologies, Inc.), the automatic product production test of 100 parts (one sheet of five sheets) of saddle stitching is repeated 50 times The In this automatic product production test, the pixel ratio per page was set to 50%, and a paper having a basis weight of 64 g / m ² was used as an image recording sheet (transfer paper). After naturally cooling the produced saddle-stitched printed matter to room temperature, all the pages of the saddle-stitched printed matter were visually checked and confirmed, and the page with the largest image loss degree of the visible image was evaluated according to the criteria shown below . In this evaluation criterion, ranks 2 to 4 are judged to be acceptable.

«Evaluation criteria»
Rank 1 (R1): Image defects such as white spots occur in the image area, and clear image transfer also occurs in the non-image area, and the document offset resistance is extremely poor. Rank 2 (R2): Paper The alignment is disturbed and the fore edge is cut with the image slightly inclined on a part of the page, or, for example, minute gloss unevenness as a trace of image adhesion occurs in some places in the image area, etc. There is a level of image loss and image transition that does not cause major problems. Rank 3 (R3): Although a crisp sound is heard when turning over a page in which the image portions overlap each other, the image and non-image portions are normal. There are no image defects and image transitions that cause practical problems in use, and excellent document offset resistance Rank 4 (R4): image area and non-image area Without at all image defects and image shift to be, anti document offset resistance is very good.

(Charge uniformity)
Charging uniformity was evaluated by halftone reproducibility. The halftone chart was copied by the above-mentioned evaluation machine, and the image density of this image was measured at five points in the axial direction of the photosensitive member and evaluated. However, the measurement of the image density was measured using an image densitometer (Macbeth RD 914). Evaluation criteria are as follows. ◎ to が are judged to pass.

«Evaluation criteria»
:: very good at less than 10% variation in concentration ○: good at greater than 10% but less than 15% variation Δ: at least 15% but less than 20% variation in concentration ×: at least 20% variation in concentration (Toner scattering)
The stress resistance (mechanical strength) of the toner was evaluated by the toner scattering evaluation. Printing of 500,000 sheets was performed using the above-mentioned evaluation machine, and the state of toner scattering was evaluated based on the degree of dirt on the hand when the user replaced the developing unit. ◎ to が are judged to pass.

«Evaluation criteria»
:: Toner scattering was not observed at all. Even if the user replaces the developing unit, his hands are not soiled at all. ○: Scattered toner adheres to the upper lid near the developing roller. Δ: Scattered toner adheres to a part of the developer upper lid. ×: User After replacing the developing unit, toner scattering is recognized as much as hand washing is necessary.

From the above results, when the toner particles of Examples and Reference Examples were used, excellent results were obtained in a well-balanced manner with respect to low temperature fixability, image storability, charge uniformity and toner scattering.

  On the other hand, when the toner particles of Comparative Examples 1 and 3 having relatively high compatibility are used, the image storability is lowered although the low temperature fixability is good. In addition, when the toner particles of Comparative Example 2 were used, although the compatibility was suppressed, the low temperature fixability and the charge uniformity decreased. Furthermore, when the toners of Comparative Examples 4 and 5 not containing the hybrid polyester resin were used, toner scattering was remarkable, and the result that the above-mentioned characteristics could not be improved in a well-balanced manner was obtained.

Claims (9)

A toner for developing an electrostatic charge image comprising a binder resin, wherein
The binder resin includes a hybrid crystalline polyester resin and an amorphous resin in which a crystalline polyester resin unit and an amorphous resin unit other than the polyester resin are chemically bonded, and the hybrid crystalline polyester The resin has a phase separation structure in which a dispersed phase is formed, and the non-crystalline resin forms a continuous phase,
Let Tm1 (° C.) be the temperature of the endothermic peak derived from the hybrid crystalline polyester resin in the first temperature rising process in differential scanning calorimetry of toner, and ΔH1 (J / g) be the endothermic amount based on the endothermic peak, 2 when the heat absorption amount based on the endothermic peak in round th heating process and [Delta] H2 (J / g), meets the following relationship formula (1) and (2),
The hybrid crystalline polyester resin is a graft copolymer,
When the carbon number of the polyhydric alcohol component constituting the crystalline polyester resin unit is C (alcohol) and the carbon number of the polyhydric carboxylic acid component constituting the crystalline polyester resin unit is C (acid), 2 ≦ | C (acid) -C (alcohol) | ≦ 10 ,
Toner for electrostatic image development.
The toner for developing an electrostatic charge image according to claim 1, wherein the temperature Tm1 (° C.) satisfies the relationship of the following formula (3).
  The electrostatic charge image development according to claim 1 or 2, wherein the content of the amorphous resin unit other than the polyester resin is 5% by mass or more and less than 10% by mass with respect to the total amount of the hybrid crystalline polyester resin. toner.   The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the non-crystalline resin unit other than the polyester resin is composed of a resin of the same type as the non-crystalline resin. Satisfy the relation below following formula (4) to (6), an electrostatic image developing toner according to any one of claims 1 to 4.
  The toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the content of the hybrid crystalline polyester resin is 30% by mass or more and less than 50% by mass with respect to the total amount of the binder resin. .   The said hybrid crystalline polyester resin is a graft copolymer which has an amorphous resin unit other than the said polyester resin as a principal chain, and has the said crystalline polyester resin unit as a side chain. A toner for developing an electrostatic charge image according to any one of the preceding claims.   The toner for electrostatic image development according to any one of claims 1 to 7, wherein the non-crystalline resin contained in the binder resin is a vinyl resin.   The toner for developing an electrostatic charge image according to any one of claims 1 to 8, wherein the non-crystalline resin unit other than the polyester resin is a vinyl resin unit.