JP2015118310A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which has excellent low-temperature fixability, gives excellent resistance to adhesion of an ejected sheet to an image formed by fast double-face printing, and suppresses image fogging in a high temperature and high humidity environment.SOLUTION: The toner includes toner particles comprising a crystalline polyester resin, a non-crystalline polyester resin, a higher fatty acid salt, and a colorant. The crystalline polyester resin has a crystal nucleating agent moiety at an end of a polyester molecular chain; the crystalline polyester resin has an SP value Spa ((cal/cm)) of 9.00 or more and 11.00 or less; and the crystal nucleating agent moiety is derived from an aliphatic monoalcohol having 10 to 30 carbon atoms and/or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms. The higher fatty acid salt has 11 to 31 carbon atoms.

Description

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

  In recent years, the level of consumer awareness of environmental impact has increased. For this reason, image forming apparatuses using electrophotography are required to further reduce power consumption. As one of the methods for reducing the power consumption of the image forming apparatus using the electrophotographic method, there is a method for reducing the power consumption in the fixing process. For this reason, the toner needs to be fixed on paper at a lower temperature than before. Generally, the toner fixing performance is related to the softening point (Tm) of the toner. Therefore, a property (so-called sharp melt property) that is quickly melted by heat during fixing is required.

  In recent years, for the purpose of imparting sharp melt properties to toners, many toners using not only amorphous resins but also crystalline resins as binder resins have been proposed. By fixing the amorphous resin and the crystalline resin in the toner at the time of fixing, the amorphous resin in the toner can be plasticized and the Tm of the toner can be lowered, so that the low temperature fixability of the toner can be improved. It has been known.

  On the other hand, there is a correlation between the Tm of the amorphous resin used for the toner and the glass transition temperature (Tg). Therefore, when Tm of the amorphous resin decreases, Tg tends to decrease, so that Tg of the toner also decreases.

  For example, Patent Document 1 improves the low-temperature fixability of the toner by using a crystalline resin that is easily compatible with the amorphous resin. However, a crystalline resin that is easily compatible with an amorphous resin has a low crystallization rate, and thus tends to have a low crystallinity. For this reason, in the toner having a low crystallinity of the crystalline resin, the crystalline resin and the amorphous resin exist in a partially compatible state, and Tg lowers due to the plasticity of the amorphous resin. As a result, when a plurality of double-sided printings are performed, there is a case in which the toner on the stacked double-sided printed image adheres (discharge ejection adhesion).

  Thus, it has been proposed to use a nucleating agent as a method for accelerating the crystallization speed of the crystalline resin. For example, in Patent Document 2, by using an organic crystal material as a nucleating agent, the crystallization speed of the crystalline resin is accelerated, and the low-temperature fixing property and the paper discharge resistance are improved. When this toner is used, for example, in an image forming apparatus with a slow printing speed capable of printing at a speed of 40 sheets / minute, the low-temperature fixing property and the paper discharge resistance can be improved. However, for example, when a high-speed image forming apparatus capable of printing at a speed of 60 sheets / min is used, a print image is stacked at a higher discharge temperature than the image forming apparatus at a speed of 40 sheets / min. Paper adhesion may occur. For this reason, it is difficult to satisfy the sheet discharge adhesion resistance in the image forming apparatus at a speed of 60 sheets / min while maintaining the low temperature fixing property equivalent to that of the image forming apparatus at a speed of 40 sheets / min. Recently, there is a demand for speeding up of image forming apparatuses, and even in high speed image forming apparatuses, there is a demand for toner having good discharge resistance adhesiveness. is there.

  Moreover, since the nucleating agent which consists of an organic type crystal material of patent document 2 tends to adsorb | suck a water | moisture content, an electrical resistance tends to fall in a high temperature, high humidity environment. For this reason, the toner containing the organic crystal material has an electrical resistance that decreases due to moisture adsorption, and the charge amount of the toner decreases. When an image is formed using such a toner having a reduced charge amount, a toner having a low charge amount is developed on the non-image portion, and thus a phenomenon called image fogging may occur. Therefore, further improvement is necessary to suppress image fogging.

JP 2002-284866 A JP 2007-79329 A

  An object of the present invention is to provide a toner that is excellent in low-temperature fixability, excellent in sheet discharge adhesion of an image printed at high speed on both sides, and suppressed in image fogging in a high-temperature and high-humidity environment.

The present invention relates to a toner having toner particles containing a crystalline polyester resin, an amorphous polyester resin, a higher fatty acid salt, and a colorant, and the crystalline polyester resin has a crystal nucleating agent moiety at the end of the molecular chain. And SPa ((cal / cm ³ ) ^1/2 ) which is the SP value of the crystalline polyester resin is 9.00 or more and 11.00 or less, and the crystal nucleating agent portion has 10 to 30 carbon atoms. The fatty acid salt is a part derived from an aliphatic monoalcohol and / or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms, and the higher fatty acid salt is a higher fatty acid salt having 11 to 31 carbon atoms. Toner.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability, excellent in sheet discharge adhesion of an image printed at high speed on both sides, and in which occurrence of image area fogging is suppressed in a high-temperature and high-humidity environment.

  After describing the effects and disadvantages of using the crystalline polyester resin, the background to the present invention will be described.

  In general, the crystalline polyester resin and the amorphous polyester resin are combined at the time of fixing the toner, so that the crystalline polyester resin plasticizes the amorphous polyester resin. As a result, the Tm of the toner is lowered and the low temperature fixability can be improved. Further, there is a correlation between Tm and Tg of the toner, and Tg tends to decrease as Tm decreases.

  On the other hand, the paper discharge adhesion occurs when the toner on the paper adheres when the paper discharge temperature exceeds the Tg of the toner. In order to suppress discharge adhesion, it is important to make the toner Tg on the paper higher than the discharge temperature. For this reason, the toner having improved low-temperature fixability with crystalline polyester resin has a lower Tg of the toner on the paper than the discharged paper temperature after fixing, which may cause a problem of paper discharge adhesion.

  In order to solve this problem, the Tg of the toner on the discharged paper needs to be higher than the discharge temperature. Therefore, the Tg of the toner on the discharged paper after fixing must be quickly returned to the Tg of the toner before plasticization. I must. For this purpose, it is necessary to quickly crystallize (increase the crystallization speed) the crystalline polyester resin compatible with the amorphous polyester resin at the time of fixing the toner. Crystallization of the crystalline polyester resin occurs when the crystalline polyester resin molecules are oriented to form crystal nuclei, and the crystalline polyester resin molecules are oriented to grow crystals based on the crystal nuclei. That is, in order to increase the crystallization speed of the crystalline polyester resin, it is necessary to (1) reduce the generation time of crystal nuclei and (2) increase the speed of crystal growth.

  Therefore, as a result of intensive studies by the present inventors, it is possible to provide a toner that is excellent in low-temperature fixability, excellent in sheet discharge adhesion of an image printed at high speed on both sides, and suppressed in image area fogging in a high-temperature and high-humidity environment. I found it.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

The present invention relates to a toner having toner particles containing a crystalline polyester resin, an amorphous polyester resin, a higher fatty acid salt, and a colorant, and the crystalline polyester resin has a crystal nucleating agent moiety at the end of the polyester molecular chain. And SPa ((cal / cm ³ ) ^1/2 ) which is the SP value of the crystalline polyester resin is 9.00 or more and 11.00 or less, and the crystal nucleating agent site has 10 to 30 carbon atoms. It is a site derived from the following aliphatic monoalcohol and / or aliphatic monocarboxylic acid having 11 to 31 carbon atoms, and the higher fatty acid salt is a higher fatty acid salt having 11 to 31 carbon atoms. Features.

  The toner particles of the present invention are particles having a weight average particle diameter (D4) of about 3.0 to 9.0 μm.

  The crystalline polyester resin, amorphous polyester resin, higher fatty acid salt, and colorant contained in the toner particles of the present invention are specifically described below.

(Crystalline polyester resin)
The toner of the present invention is characterized by having a crystal nucleating agent moiety at the end of the molecular chain of the crystalline polyester resin and using a higher fatty acid salt in combination. By using these two in combination, the Tg of the toner plasticized at the time of fixing can be quickly returned to the Tg of the toner before plasticization, and excellent discharge resistance and low temperature fixing properties can be achieved even in high-speed image forming apparatuses. Can be compatible. Although this reason is not certain, the present inventors consider as follows.

  At the time of fixing, the toner is in a molten state, cooled after fixing, and fixed on paper. Therefore, the toner on the paper after fixing starts to crystallize from a component having a high melting point during cooling. Therefore, by using together a higher fatty acid salt having a melting point higher than that of the crystalline polyester resin, the higher fatty acid salt generates a crystal nucleus before the crystalline polyester resin generates a crystal nucleus. Therefore, the generation time of crystal nuclei is shortened as compared with a system using only a crystalline polyester resin as a crystalline component.

  Furthermore, it is thought that the crystal growth speed is improved by orienting the crystal nucleating agent site at the end of the molecular chain of the crystalline polyester resin of the present invention with respect to this crystal nucleus. This is because the crystalline polyester resin is compatible with the amorphous polyester resin, but the crystal nucleating agent site at the end of the molecular chain is low in polarity and thus is hardly compatible with the amorphous polyester resin. On the other hand, the crystal nucleating agent site at the molecular chain end of the crystalline polyester resin and the crystal nucleus of the higher fatty acid salt are close in polarity. For this reason, the crystalline nucleating agent site at the molecular chain end of the crystalline polyester resin is easily oriented to the crystal nucleus of the higher fatty acid salt, so that the crystalline polyester resin is successively oriented to the crystal nucleus. Therefore, the crystal growth speed is improved by having a crystal nucleating agent site at the end of the molecular chain of the crystalline polyester resin and using a higher fatty acid salt in combination.

  Therefore, the toner of the present invention can not only shorten the generation time of crystal nuclei in the toner but also improve the crystal growth speed of the crystalline polyester resin, so that the crystallization speed can be improved. As a result, the Tg of the toner, which has been lowered due to the plastic effect of the crystalline polyester resin, can be quickly returned, so that both sheet discharge resistance and low-temperature fixability can be achieved.

  On the other hand, in a system in which a conventional crystalline polyester resin and a higher fatty acid are used in combination, the higher fatty acid salt becomes a crystal nucleus, so that the generation time of the crystal nucleus can be shortened. However, since the speed of crystal growth of the crystalline polyester resin is determined by the ease of orientation of the crystalline polyester resin molecules to the crystal nucleus, the speed of crystal growth of the crystalline polyester resin molecules should be improved. I can't. Therefore, since the crystallization speed cannot be improved as much as the toner of the present invention, it takes time to return the Tg of the toner, which has been lowered by the plasticizing effect of the crystalline polyester resin, to the Tg of the toner before plasticization. Further, when such toner is used, in a low-speed image forming apparatus, the discharge temperature becomes lower than the Tg of the toner before the discharged sheets after fixing are stacked. Had sex. However, in the high-speed image forming apparatus, the discharge sheets are stacked before the discharge temperature becomes lower than the Tg of the toner.

  Further, in the toner of the present invention, the crystalline nucleating agent site at the molecular chain end of the crystalline polyester resin is an aliphatic monoalcohol having 10 to 30 carbon atoms and / or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms. It is a site derived from.

  The toner of the present invention has a crystal nucleus agent site of an alkyl chain having 10 or more carbon atoms (that is, 10 or more carbon atoms in the case of an aliphatic monoalcohol and 11 or more carbon atoms in the case of an aliphatic monocarboxylic acid). Improved resistance to paper ejection. The present inventors consider this reason as follows. Since the polarity of the molecular chain at the end of the crystalline polyester resin is close to the polarity of the higher fatty acid salt because the crystal nucleating agent site is an alkyl chain having 10 or more carbon atoms, the crystalline polyester resin is a crystalline nucleus of the higher fatty acid salt. It becomes easy to orient. As a result, since the crystal growth of the crystalline polyester resin can be accelerated, it is considered that the crystallization speed of the crystalline polyester resin is improved and the sheet discharge resistance is improved.

  On the other hand, when the carbon number of the alkyl chain at the crystal nucleating agent site exceeds 30 (that is, when aliphatic monoalcohol exceeds 30 carbon atoms, when aliphatic monocarboxylic acid exceeds 31 carbon atoms), Since the polarity of the molecular chain terminal of the crystalline polyester resin becomes too low, the charge amount of the toner may decrease. For this reason, there is a possibility that image portion fogging due to low charge amount toner occurs.

  Further, from the viewpoint of increasing the crystallization rate of the crystalline polyester resin, the crystal nucleating agent site is 0.1 mol or more, 7.0 mol or less, preferably 0.4 mol or more, preferably 4. It is preferably contained in 0 mol or less. A method for determining whether or not the crystal nucleating agent site is bonded to the crystalline polyester resin will be described later.

Furthermore, the toner of the present invention is characterized in that the crystalline polyester resin has an SPa value (cal / cm ³ ) ^1/2 of 9.00 or more and 11.00 or less.

  In the crystalline polyester resin, a small SP value indicates that the chain length of the alkyl group of the aliphatic alcohol unit and the aliphatic carboxylic acid unit constituting the crystalline polyester resin is long. A crystalline polyester resin composed of a component having a long chain length of an alkyl group has a small amount of polar groups, so that the charge amount of the toner is low. Therefore, when the SPa value is less than 9.00, there is a concern that image fogging may occur due to a decrease in the toner charge amount. On the other hand, when the SPa value is larger than 11.00, the polar groups in the crystalline polyester resin increase, so that the hygroscopic property of the crystalline polyester resin increases and the hygroscopic property of the toner also increases. Since the toner having high hygroscopicity has a low electric resistance value in a high temperature and high humidity environment, the toner charge amount is lowered by leaving it in such an environment. Therefore, there is a concern that image fogging occurs. The SPa value is preferably 9.18 or more and 10.87 or less.

  Note that the SP value used in the present invention is a commonly used Fedors method [Poly. Eng. Sci. , 14 (2) 147 (1974)], the value calculated from the type and ratio of the monomers constituting the resin. The SPa value of the crystalline polyester resin represents the SP value of the polyester molecular chain including the crystal nucleating agent site.

Further, it is preferable that the SPa value of the crystalline polyester resin and the SPb of the amorphous polyester resin contained in the toner of the present invention satisfy the following formula (1).
−1.00 ≦ SPb−SPa ≦ 0.80 (1)
Further, the value of “SPb−SPa” is more preferably −0.93 or more, and more preferably 0.78 or less.

  The SP value (solubility parameter) is used as an index indicating the ease of mixing of resins. The value of “SPb−SPa” is an index indicating the compatibility of the crystalline polyester resin and the amorphous polyester resin when the toner is melted by heat. By controlling the SP value of each resin within this range, it is possible to further improve the toner low-temperature fixability and paper discharge resistance.

  Examples of the crystalline polyester resin and the amorphous polyester resin used in the toner of the present invention include the following.

[Raw material for crystalline polyester resin]
The crystalline polyester resin is a resin having a polyhydric alcohol unit and a polycarboxylic acid unit. As the alcohol component used as the raw material of the polyhydric alcohol unit, it is preferable to use an aliphatic diol having 6 to 18 carbon atoms from the viewpoint of enhancing the crystallinity of the crystalline polyester resin. Among these, aliphatic diols having 6 to 12 carbon atoms are preferable from the viewpoint of low-temperature fixability of the toner and sheet discharge adhesion resistance. Examples of the aliphatic diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, Examples include 12-dodecanediol. The content of the aliphatic diol is preferably 80.0 mol% or more and 100.0 mol% or less in the alcohol component from the viewpoint of further improving the crystallinity of the crystalline polyester resin.

  As an alcohol component, you may contain polyhydric alcohol components other than said aliphatic diol, for example, the following are mentioned. Bisphenol represented by the following chemical formula (I), including polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane, and the like Aromatic diols such as alkylene oxide adducts of A; trihydric or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane.

  In the above formula, R represents an alkylene group having 2 or 3 carbon atoms. x and y are positive numbers, and the sum of x and y is 1 or more and 16 or less, preferably 1.5 or more and 5 or less.

  As a carboxylic acid component used as a raw material of the polyvalent carboxylic acid unit, an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferable. Among these, an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms is preferable from the viewpoint of toner fixing properties and paper discharge resistance. Examples of the aliphatic dicarboxylic acid compound include 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, and the like. It is done. The content of the aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferably 80.0 mol% or more and 100.0 mol% or less in the carboxylic acid component.

  As a carboxylic acid component, you may contain carboxylic acid components other than the said aliphatic dicarboxylic acid compound. For example, an aromatic dicarboxylic acid compound, a trivalent or higher valent aromatic polycarboxylic acid compound, and the like can be mentioned, but the invention is not particularly limited thereto. The aromatic dicarboxylic acid compound also includes an aromatic dicarboxylic acid derivative. Specific examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters thereof. . Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and aromatic carboxylic acids such as pyromellitic acid, and these Derivatives such as acid anhydrides and alkyl (having 1 to 3 carbon atoms) esters may be mentioned.

  The molar ratio of the alcohol component and carboxylic acid component (carboxylic acid component / alcohol component) used as the raw material monomer of the crystalline polyester resin is preferably 0.80 or more and 1.20 or less.

  The weight average molecular weight Mw of the crystalline polyester resin is preferably 8000 or more and 100,000 or less, and preferably 12,000 or more and 45,000 or less, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. More preferred.

  The crystalline polyester resin preferably has a heat of fusion (ΔH) determined from the area of the endothermic peak observed at the time of temperature rise in differential scanning calorimeter (DSC) measurement, from 100 J / g to 140 J / g. Further, the melting point of the crystalline polyester resin is preferably 60 ° C. or higher and 120 ° C. or lower, more preferably 70 ° C. or higher and 90 ° C. or lower, from the viewpoint of low-temperature fixability of the toner.

  The acid value of the crystalline polyester resin is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of good charging characteristics of the toner.

[Raw material of amorphous polyester resin]
The amorphous polyester resin is a resin having a polyhydric alcohol unit and a polyvalent carboxylic acid unit. The following are mentioned as an alcohol component used for the raw material of a polyhydric alcohol unit. The following are mentioned as a bivalent alcohol component. 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct, 2,2-bis (4-hydroxyphenyl) propane polyoxyethylene adduct, and the like represented by the above formula (I) A alkylene oxide adduct of A, ethylene glycol, 1,3-propylene glycol, neopentyl glycol and the like. Examples of the trivalent or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol, and the like. The divalent alcohol component and the trihydric or higher polyhydric alcohol component can be used singly or in combination of two or more.

  Moreover, the following are mentioned as a carboxylic acid component used for the raw material of a polyvalent carboxylic acid unit. Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, n-dodecenyl succinic acid, anhydrides of these acids, and lower alkyl esters. It is done. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, emporic trimer acid and acid anhydrides thereof, lower Examples include alkyl esters.

  In the condensation polymerization of the amorphous polyester resin, a known esterification catalyst such as dibutyltin oxide may be used as appropriate in order to promote the reaction.

  The weight average molecular weight Mw of the amorphous polyester resin is preferably 8000 or more and 100,000 or less, from 40,000 or more and 300,000 or less, from the viewpoint of low-temperature fixability and discharge resistance of the toner. More preferably.

  The acid value of the amorphous polyester resin is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of the charging characteristics of the toner.

  The mass ratio of the crystalline polyester resin and the amorphous polyester resin contained in the toner is preferably 5:95 to 40:60 from the viewpoint of low-temperature fixability and discharge resistance of the toner. .

[Higher fatty acid salt]
Next, the higher fatty acid salt used in the present invention will be described.

  The toner of the present invention is characterized by containing a higher fatty acid salt having 11 to 31 carbon atoms. When the number of carbon atoms of the higher fatty acid salt is less than 11, the melting point of the higher fatty acid salt is lowered, so that the time required for generating crystal nuclei becomes longer. For this reason, since the crystallization speed of the crystalline polyester resin is not improved, it is difficult to satisfy the toner discharge resistance. Further, when the number of carbon atoms of the higher fatty acid salt exceeds 31, the polarity of the higher fatty acid salt becomes low, and it becomes difficult to uniformly disperse the higher fatty acid salt in the toner. Therefore, the number of crystal nuclei existing in the toner is reduced. Since the crystalline polyester resin grows from the crystal nucleus, the number of the crystalline polyester resin that can grow the crystal is reduced by reducing the number of crystal nuclei. As a result, the crystal growth is slowed down. For this reason, when the number of carbon atoms of the higher fatty acid salt exceeds 31, the crystallization speed decreases, so that it is difficult to satisfy the discharge resistance of the toner.

Moreover, it is preferable that carbon number Cm of the crystal nucleating agent site | part of this invention and carbon number Cn of a higher fatty acid salt satisfy following Numerical formula (2).
−12 ≦ Cm−Cn ≦ 12 (2)
By setting the value of “Cm−Cn” to −12 or more and 12 or less, the polarity of the crystal nucleating agent site and the polarity of the higher fatty acid salt can be made closer. As a result, the crystallization speed of the crystalline polyester resin can be further improved, which is preferable from the viewpoint of toner discharge resistance. Further, from the viewpoint of the discharge resistance adhesion of the toner, the value of “Cm−Cn” is more preferably −8 or more, and more preferably 8 or less.

  Furthermore, since the toner of the present invention has a crystal nucleating agent moiety at the molecular chain terminal of the crystalline polyester resin, the charge amount of the toner when left in a high temperature and high humidity environment even when used in combination with a higher fatty acid salt The decrease can be suppressed. The reason is as follows.

  Since it has a crystal nucleating agent site at the molecular chain terminal of the crystalline polyester resin, the crystal nucleus of the higher fatty acid salt is covered with a crystal nucleating agent site having a lower polarity than the crystalline polyester resin. Therefore, the hygroscopic property of the higher fatty acid salt is inhibited by the crystal nucleating agent site covering the crystal surface, and the hygroscopic property of the higher fatty acid salt is lowered. As a result, the hygroscopicity of the toner also decreases. Therefore, since the toner charge amount can be prevented from lowering even when left in a high temperature and high humidity environment, image fogging can be suppressed.

  In a toner containing a conventional crystalline polyester resin and a higher fatty acid salt, the crystalline polyester resin crystal covers the crystal nucleus of the higher fatty acid salt with the end of the crystalline polyester resin. There are polar groups derived from the ends of the polyester resin. Therefore, the effect of inhibiting the hygroscopicity of higher fatty acid salts is weaker than when a crystalline polyester resin having a crystal nucleating agent moiety at the molecular chain end is used. In some cases, the amount of electrification was reduced.

  Furthermore, it is preferable that the higher fatty acid salt of the present invention is a higher fatty acid metal salt, and the valence of the metal ion of the higher fatty acid metal salt is 2 or more. The reason for this is that it is easier to cover the crystal nuclei of the higher fatty acid salt with the crystal nucleating agent part of the crystalline polyester resin. Because it can.

  Examples of the higher fatty acid salt used in the toner of the present invention include the following. Examples of the fatty acid include fatty acids having 11 to 31 carbon atoms, preferably 16 to 26 carbon atoms, and may be saturated, unsaturated, linear or branched, and linear fatty acids are particularly preferable. Lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid are preferred, and stearic acid is particularly preferred. Examples of the metal that binds to these fatty acids include sodium, calcium, magnesium, zinc, and aluminum. Bivalent or higher metal such as calcium, magnesium, zinc, and aluminum are preferable. Aluminum is particularly preferable.

  Further, the content of the higher fatty acid salt is preferably 15 parts by mass or less with respect to 100 parts by mass of the crystalline polyester resin, from the viewpoint of suppressing a decrease in the charge amount of the toner in a high temperature and high humidity environment. It is more preferably 0 parts by mass or more and 10.0 parts by mass or less.

  In addition, it is preferable that the higher fatty acid salt has a melting point equal to or higher than the melting point of the crystalline polyester resin in terms of shortening the generation time of crystal nuclei.

[Colorant]
Examples of the colorant used in the toner of the present invention include the following.

  Examples of the color pigment for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

  Examples of the color pigment for cyan toner include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the coloring dye for cyan include C.I. I. There is Solvent Blue 70.

  Examples of the color pigment for yellow include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20

  Examples of the coloring dye for yellow include C.I. I. There is Solvent Yellow 162.

  Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

  The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin.

  The toner of the present invention may be a magnetic toner. When used as a magnetic toner, it is preferable to use magnetic iron oxide as the magnetic material and colorant. As the magnetic iron oxide, iron oxides such as magnetite, maghematite, and ferrite are used. The amount of magnetic iron oxide contained in the toner is preferably 25 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin.

〔wax〕
Further, the toner of the present invention may contain a wax as necessary, and examples thereof include the following. The wax is preferably a hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, or paraffin wax from the viewpoint of easy dispersion in the toner and high releasability. If necessary, two or more kinds of waxes may be used in combination.

  Specific examples of the wax include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries); High wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ); Sazol H1, H2, C80, C105, C77 (Schumann Sazol); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.); Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Adre Co., Ltd.); wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Available at Celerica NODA).

  When the toner is produced by a pulverization method, the wax is preferably added at the time of melt kneading. The wax preferably contains 0.1 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin.

[Flowability improver]
The toner of the present invention may contain a fluidity improver such as an inorganic fine powder. As the inorganic fine powder for improving fluidity, inorganic fine powder such as silica, titanium oxide and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof. The inorganic fine powder preferably has a specific surface area of 10 m ² / g or more and 400 m ² / g or less. In addition, inorganic fine particles having a specific surface area in the above range may be used in combination.

  The inorganic fine powder is preferably used in an amount of 0.1 parts by mass or more and 8.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the inorganic fine powder.

[Other external additives]
If necessary, other external additives may be added to the toner. For example, charging aids, conductivity imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, resin fine particles and inorganic fine particles that function as abrasives. Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Of these, polyvinylidene fluoride powder is preferred. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder.
[Magnetic carrier]
The toner of the present invention can be used as a one-component developer, but can also be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, a known carrier such as a ferrite carrier or a magnetic material-dispersed resin carrier (so-called resin carrier) in which a magnetic material is dispersed in a binder resin can be used. When the toner is mixed with a magnetic carrier and used as a two-component developer, the toner concentration in the developer is preferably 2% by mass or more and 15% by mass or less.

[Toner Production Method]
The method for producing the toner of the present invention is not particularly limited, but a pulverization method is preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability. Hereinafter, a method for obtaining the toner of the present invention by the pulverization method will be described.

  In the raw material mixing step, a crystalline polyester resin, an amorphous polyester resin, a higher fatty acid salt, a colorant, other additives, and the like are weighed in a predetermined amount and mixed as materials constituting the toner particles. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse the crystalline polyester resin, higher fatty acid salt, colorant and the like in the amorphous polyester resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders have become mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by K.C.K. ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer. Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  If necessary, after pulverization, using a hybridization system (manufactured by Nara Machinery Co., Ltd.), mechano-fusion system (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron), Meteorenbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) It is also possible to perform surface treatment of toner particles such as spheroidization. Furthermore, if necessary, desired additives can be sufficiently mixed by a mixer such as a Henschel mixer.

〔Evaluation method〕
A method for measuring various physical properties of the toner and raw materials will be described below. The physical property values are also measured based on these methods in Examples and the like described later.

<1. Measurement of site of crystal nucleating agent>
2 mg of a resin sample is precisely weighed, and 2 ml of chloroform is added and dissolved to prepare a sample solution. As the resin sample, a crystalline polyester resin having a crystal nucleating agent site is used. Next, 20 mg of 2,5-dihydroxybenzoic acid (DHBA) is precisely weighed, and 1 ml of chloroform is added and dissolved to prepare a matrix solution. In addition, after accurately weighing 3 mg of sodium trifluoroacetate (NaTFA), 1 ml of acetone is added and dissolved to prepare an ionization aid solution.

  25 μl of the sample solution thus prepared, 50 μl of the matrix solution, and 5 μl of the ionization aid solution are mixed, dropped onto a sample plate for MALDI analysis, and dried to obtain a measurement sample. As an analytical instrument, MALDI-TOFMS (Reflex III manufactured by Bruker Daltonics) is used to obtain a mass spectrum. In the obtained mass spectrum, assignment of each peak in the oligomer region (m / Z is 2000 or less) is performed, and it is confirmed whether or not a peak corresponding to a structure in which a crystal nucleating agent is bonded to the molecular end exists.

<2. Measurement of resin weight average molecular weight by GPC>
The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used, and at least about 10 standard polystyrene samples are used. The detector uses an RI (refractive index) detector. In addition, as a column, it is good to combine several commercially available polystyrene gel columns, for example, the following combinations are mentioned. Showa Denko Co., Ltd. of shodex GPC KF-801,802,803,804,805,806,807,800P of the combination and, Tosoh Corp. of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H (H XL) , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgourd column combination.

  Moreover, a sample is produced as follows.

  Place the sample in THF and leave it at 25 ° C. for several hours, then shake it well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. Note that the total standing time in THF is 24 hours. Then, a sample processing filter (pore size of 0.2 μm or more and 0.5 μm or less, for example, Myssho Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 mg / ml or more and 5.0 mg / ml or less.

<3. Measurement of melting point and heat of fusion of crystalline polyester resin, higher fatty acid salt and wax>
The melting point of the crystalline polyester resin, higher fatty acid salt and wax is the peak temperature of the maximum endothermic peak in a DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). Is the melting point, and the amount of heat obtained from the peak area is the heat of fusion (J / g).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again.

  The maximum endothermic peak temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point, and the amount of heat obtained from the peak area is defined as the heat of fusion.

<4. Measurement of Tg of Amorphous Polyester Resin>
The Tg of the amorphous polyester resin C is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The temperature correction of the apparatus detection unit, the amount of sample used, and the temperature raising condition are the same as those in the case of the “measurement of melting point and heat of fusion”.

  A specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the amorphous polyester resin.

<5. Measurement of softening point of amorphous polyester resin and toner>
The softening point of the amorphous polyester resin and toner is measured using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston descends at this time. A flow curve showing the relationship between quantity and temperature can be obtained.

  The “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation device Flow Tester CFT-500D” is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, a value X that is a half of the difference between the piston lowering amount Smax when the outflow is finished and the piston lowering amount Smin when the outflow starts is obtained (X = (Smax−Smin) / 2). In the flow curve, the temperature of the flow curve when the piston lowering amount is “Smin + X” is the melting temperature in the 1/2 method.

  As a measurement sample, a sample of about 1.0 g was compression-molded at about 10 MPa for about 60 seconds at 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System). A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method.
Temperature increase rate: 4 ° C./min.
Starting temperature: 50 ° C.
Achieving temperature: 200 ° C
Piston cross-sectional area: 1.000 cm ² .
Test load (piston load): 10.0 kgf (0.9807 MPa).
Preheating time: 300 seconds.
Die hole diameter: 1.0 mm.
Die length: 1.0 mm.

<6. Measurement of acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the pulverized polyester resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

  (3) The acid value is calculated by substituting the obtained result into the following formula.

A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<5. Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analyze and calculate.

  As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in deionized water to a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked. In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

Specific measurement methods are as follows (1) to (7).
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. The dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder having a pH of 7 is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for cleaning precision instruments (made by Wako Pure Chemical Industries, Ltd.) 3 times by weight with deionized water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of deionized water is added, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be described with reference to production examples and examples. Production Examples 1 to 19 are production examples of crystalline polyester resins, and Production Examples 21 to 24 are production examples of amorphous polyester resins. In the following description, the number of parts is based on parts by mass.

<Production Example 1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1,10-decanediol as an alcohol monomer and sebacic acid as a carboxylic acid monomer in the amounts shown in Table 1 (49 mol% each). I put it in. Then, 1.5 parts by mass of tin dioctylate as a catalyst was added to 100 parts by mass of the total amount of raw material monomers, heated to 150 ° C. in a nitrogen atmosphere, and reacted for 6 hours while distilling off water at normal pressure. . Next, the reaction was carried out while increasing the temperature up to 200 ° C. at 10 ° C./hour. After reaching 210 ° C., the reaction was carried out for 2 hours, and then the reaction vessel was depressurized to 5 kPa or less and reacted at 210 ° C. for 3 hours. A resin was obtained.

  Thereafter, the pressure in the reaction vessel was gradually released to return to normal pressure, and then the amount (2 mol%) of a crystal nucleating agent (stearic acid) shown in Table 1 was added, and the mixture was heated at 210 ° C. for 2 hours under normal pressure. Reacted. Thereafter, the inside of the reaction vessel was again depressurized to 5 kPa or less and reacted at 210 ° C. for 2 hours. 1 was obtained. In the MALDI-TOFMS mass spectrum of the obtained crystalline polyester resin, the peak of the structure in which stearic acid was bonded to the molecular terminal of the crystalline polyester resin was confirmed. It was confirmed that the agent was bound. Crystalline polyester resin no. The physical properties of 1 are shown in Table 2.

<Production Examples 2 to 19>
The type and amount of the monomer and crystal nucleating agent were changed as shown in Table 1, and the rest was the same as in Production Example 1 except that the crystalline polyester resin No. 1 was used. 2 to No. 19 was obtained. In addition, in the MALDI-TOFMS mass spectra of the resins obtained in Production Examples 2 to 17, a peak of a structure in which a crystal nucleating agent is bonded to the molecular end is confirmed, and the molecular end and the crystal nucleating agent are bonded. confirmed. Production Examples 18 and 19 are production examples in which no crystal nucleating agent is used. Table 2 shows the physical properties of these crystalline polyester resins.

<Production Example 21>
Into a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the amount of monomer shown in Table 3 was added, and then dibutyltin was added as a catalyst to 1.5 parts by mass with respect to 100 parts by mass of the total amount of monomers. Part was added. Next, the temperature was quickly raised to 190 ° C. at normal pressure in a nitrogen atmosphere, and then water was distilled off while raising the temperature from 190 ° C. to 220 ° C. at a rate of 10 ° C./hour to perform polycondensation. After reaching 220 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 220 ° C. and 5 kPa or less. 21 was obtained. At that time, the obtained polyester resin No. The polymerization time was adjusted so that the softening point of 21 was the value shown in Table 4. Amorphous polyester resin No. Table 4 shows the physical properties of 21.

<Production Examples 22 to 24>
The type and amount used of the monomer were changed as shown in Table 3, and other than that, the amorphous polyester resin No. 1 was prepared in the same manner as in Production Example 21. 22 thru | or No. 24 was obtained. Table 4 shows the physical properties of these amorphous polyester resins.

<Example 1>
The materials shown in Table 5 below were mixed in a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Kako Co., Ltd.) and then rotated in a twin-screw kneader (PCM-30 type manufactured by Ikekai Tekko Co., Ltd.). It knead | mixed on the conditions of several 3.3 / second and the kneading | mixing temperature of 130 degreeC. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Kogyo Co., Ltd.). Further, the finely pulverized powder thus obtained was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles having a weight average particle diameter of 7.0 μm.

  To 100.0 parts by mass of the obtained toner particles, 1.0 part by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm and surface-treated with a 15.0% by mass solution of isobutyltrimethoxysilane and 20.0 parts by mass of hexamethyldisilazane. 0.8 parts by weight of hydrophobic silica fine particles having a primary average particle diameter of 16 nm surface-treated with a% solution, and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Got. Various physical properties of the toner were measured according to the evaluation method. Table 6 shows the evaluation results. Further, toner performance was evaluated according to the following methods (1) to (4).

<Evaluation>
(1) Evaluation of low-temperature fixability A commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP) was used. The fixing device was removed from the evaluation machine, and an external fixing device that can arbitrarily set the fixing temperature, the fixing nip pressure, and the process speed was attached. As the recording medium, high white paper GF-C081 (manufactured by Canon Marketing Japan, 81.4 g / m ² ) was used. The product toner was extracted from a commercially available black cartridge, the interior was cleaned by air blow, and 150 g of toner 1 was filled. In each of the magenta, yellow, and cyan stations, product toner was extracted, and magenta, yellow, and cyan cartridges with the remaining toner amount detection mechanism disabled were inserted.

In an environment of a temperature of 23 ° C. and a relative humidity of 50%, a solid black unfixed image was output so that the applied toner amount was 0.6 mg / cm ² . The fixing temperature of the fixing device was changed to 130 ° C., the fixing nip pressure was changed to 0.10 MPa, and the process speed was increased every 20 mm / sec in the range from 200 mm / sec to 400 mm / sec. Was fixed.

The obtained solid black image was rubbed 5 times with Sylbon paper applied with a load of about 100 g, and the point at which the density reduction rate of the image density before and after the rub was 10% or less was set as the maximum process speed at which fixing can be performed. The faster the maximum process speed that can be fixed, the better the low-temperature fixability during high-speed development. Table 7 shows the evaluation results. The evaluation results are ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A (very good): The maximum process speed capable of fixing is 400 mm / sec or more. (60 sheets or more)
B (good): The maximum process speed capable of fixing is 300 mm / sec or more and less than 400 mm / sec. (60 sheets machine)
C (Normal): The maximum process speed capable of fixing is 200 mm / sec or more and less than 300 mm / sec. (40 sheets machine)
D (Poor): The maximum process speed that can be fixed is less than 200 mm / sec.

(2) Paper discharge resistance in double-sided printing A commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP) was used. As the recording medium, high white paper GF-C081 (manufactured by Canon Marketing Japan, 81.4 g / m ² ) was used. The product toner was extracted from a commercially available black cartridge, the interior was cleaned by air blow, and 150 g of toner 1 was filled. In each of the magenta, yellow, and cyan stations, product toner was extracted, and magenta, yellow, and cyan cartridges with the remaining toner amount detection mechanism disabled were inserted.

Under an environment of a temperature of 30 ° C. and a relative humidity of 80%, ten solid black images were output by double-sided printing so that the applied toner amount was 0.6 mg / cm ² . After the output of 10 sheets, a load of about 2 kg was applied on the paper with the output images superimposed, and left for 10 minutes. After leaving for 10 minutes, the printed images were evaluated for each sheet for adhesion. The results were ranked A to C according to the following criteria, but in the present invention, up to rank B is an acceptable level.
A: There is no bonded image and good image quality is maintained.
B: Although there are adhered images, they are easily separated and maintain good image quality.
C: There is a bonded image, and there is an image defect after separation.

(3) Paper discharge resistance in high-speed double-sided printing In the commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP), the fixing process speed, the developing process speed, and the paper passing interval are changed, and the speed is 60 sheets / min. Modified to print. Using this modified device, the paper discharge resistance was evaluated in the same manner as in (2) above. The results were ranked A to C according to the following criteria, but in the present invention, up to rank B is an acceptable level.
A: There is no bonded image and good image quality is maintained.
B: Although there are adhered images, they are easily separated and maintain good image quality.
C: There is a bonded image, and there is an image defect after separation.

(4) Image fogging evaluation The same evaluation paper and toner cartridge as those in (2) above were prepared. Under an environment of a temperature of 23 ° C. and a relative humidity of 50%, development conditions were set such that the applied amount of toner was 0.3 mg / cm ² for a solid black image, and 10 solid white images were printed. The initial image fogging was evaluated for the 10th solid white image. Further, after this toner cartridge was allowed to stand for 3 days and 3 nights, one solid white image was printed under the same development conditions as in the initial image fogging evaluation, and the image fogging after being allowed to stand was evaluated. Further, even in an environment of a temperature of 30 ° C. and a relative humidity of 80%, the same evaluation was performed by setting the development conditions so that the toner loading amount was 0.3 mg / cm ² for a solid black image.

Image fogging was evaluated by measuring reflectance (%) using a digital white photometer (TC-6D type, manufactured by Tokyo Denshoku Co., Ltd., using a green filter). The content of the evaluation was obtained by subtracting the reflectance (%) of the blank paper portion after printing from the reflectance (%) of the paper that did not pass through the evaluator. The lower the image fog (%), the better the image fog. The results were ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A: Image fog (%) is less than 0.5%.
B: Image fog (%) is 0.5% or more and less than 1.0%.
C: Image fog (%) is 1.0% or more and less than 1.5%.
D: Image fog (%) is 1.5% or more.

  With respect to the toner 1, any of the above evaluations (1) to (4) gave good results.

<Examples 2 to 24, Reference Example 25, and Comparative Examples 1 to 6>
Toners 2 to 31 were obtained in the same manner as in Example 1 except that the types and amounts used of the crystalline polyester resin, amorphous polyester resin and higher fatty acid salt were changed to the conditions shown in Table 6. It was. The physical properties and performance evaluation of each toner obtained were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 6 and 7.

  Comparative Examples 1 and 2 are examples in which the carbon number of the higher fatty acid salt does not satisfy the requirements of the present invention. Comparative Examples 3 and 4 are examples in which the SPa value of the crystalline polyester resin does not satisfy the requirements of the present invention. Comparative Examples 5 and 6 are examples using a crystalline polyester resin having no crystal nucleating agent site at the end of the molecular chain. In Reference Example 25, the acid / alcohol symmetry of the crystalline polyester resin is very high, and it further has a crystal nucleating agent site. Therefore, it is expected that the crystal growth rate is relatively fast compared to other crystalline polyester resins. Is done. For this reason, it is considered that even if a higher fatty acid salt is not used, it has reached a level where there is no problem in the evaluation criteria in the present invention.

  Further, Comparative Examples 1, 2, 5, and 6 are considered to have poor sheet discharge adhesion resistance because the crystal growth of the crystalline polyester resin based on the crystal nucleus of the higher fatty acid salt is slow. Since Comparative Example 3 tends to separate from the amorphous polyester resin, it is considered that the plastic effect by the crystalline polyester resin did not appear when the fixing test was performed at high speed. In Comparative Example 4, since the crystalline polyester resin has a high polarity, it is considered that moisture adsorption is high and image fogging occurs in a high temperature and high humidity environment.

In addition, SP value used by this invention is a value calculated from the kind and ratio of the monomer which comprise resin by the method generally used . The SPa value of the crystalline polyester resin represents the SP value of the polyester molecular chain including the crystal nucleating agent site.

Claims (4)

In a toner having toner particles containing a crystalline polyester resin, an amorphous polyester resin, a higher fatty acid salt, and a colorant,
The crystalline polyester resin has a crystal nucleating agent site at the end of the molecular chain, and SPa ((cal / cm ³ ) ^1/2 ) of the crystalline polyester resin is 9.00 or more and 11. 00 or less,
The crystal nucleating agent site is a site derived from an aliphatic monoalcohol having 10 to 30 carbon atoms and / or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms,
The toner, wherein the higher fatty acid salt is a higher fatty acid salt having 11 to 31 carbon atoms. The SPa of the crystalline polyester and SPb ((cal / cm ³ ) ^1/2 ), which is the SP value of the amorphous polyester resin, satisfy the following mathematical formula (1). toner.
−1.00 ≦ SPb−SPa ≦ 0.80 (1) 3. The toner according to claim 1, wherein a carbon number Cm of the crystal nucleating agent portion and a carbon number Cn of the higher fatty acid salt satisfy the following mathematical formula (2).
−12 ≦ Cm−Cn ≦ 12 (2)   The toner according to claim 1, wherein the higher fatty acid salt is a higher fatty acid metal salt, and a valence of a metal ion of the higher fatty acid metal salt is 2 or more.