JP2018200356A - Toner and toner manufacturing method - Google Patents

Abstract

To provide toner having a high tinctorial power and an appropriate electrification characteristic.SOLUTION: Toner including toner particles having crystals of binder resin and copper phthalocyanine is provided. In X-ray diffraction by a CuKα ray, the crystal of the copper phthalocyanine includes a diffraction peak of a half value width of 0.30° or more and 0.34° or less in the range of a bragg angle (2θ±0.20°) of 6.50° or more and 7.50° or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a toner used in an electrophotographic image forming apparatus.

  Particularly important properties for the toner are moderate chargeability and good tinting strength, and that they are stable over time. For this purpose, it is preferable that the colorant is uniformly and finely dispersed in the binder resin in the toner particles.

  Currently, copper phthalocyanine, which is a kind of pigment, is suitably used as a colorant for cyan toner. Copper phthalocyanine has excellent performance in terms of cost and light resistance.

  However, since copper phthalocyanine has strong crystallinity and tends to have a strong cohesion between copper phthalocyanine crystal particles, dispersion in a medium such as an organic solvent or a molten resin tends to be insufficient. When the dispersibility of the copper phthalocyanine crystal particles is insufficient, the coloring power of the toner and the chargeability are liable to be reduced.

  Patent Document 1 discloses a technique using a polymer having units derived from sodium styrenesulfonate as a pigment dispersant as a technique for improving the dispersibility of copper phthalocyanine crystal particles in toner particles of cyan toner. .

  Patent Document 2 discloses a technique for improving the pigment dispersibility in toner particles by containing a copper phthalocyanine derivative in the toner particles.

  In Patent Documents 3 and 4, as a technique that does not use a pigment dispersant, a method of performing a master batch process by mixing a pigment with a part of a binder resin, or a paste containing water in a pigment, A method for suppressing particle growth is disclosed.

  However, in any of these techniques, there is room for improvement with respect to the dispersibility of the copper phthalocyanine crystal particles in the toner particles and the coloring power and chargeability of the toner.

Japanese Patent Laid-Open No. 03-113462 JP 2004-341397 A Japanese Patent Laid-Open No. 06-130724 Japanese Patent Laid-Open No. 08-314180

  An object of the present invention is to provide a toner having good coloring power and appropriate chargeability.

The present invention is a toner having toner particles containing a binder resin and copper phthalocyanine crystals,
The X-ray diffraction of the copper phthalocyanine crystal shows a Bragg angle (2θ ± 0.20 °) in the range of 6.50 ° to 7.50 ° and a half width of 0.30 ° to 0.000. A toner having a diffraction peak of 34 ° or less.

  According to the present invention, it is possible to provide a toner having good coloring power and appropriate chargeability.

It is a figure which shows an example of the biaxial extruder used for this invention.

The toner of the present invention is a toner having toner particles containing a binder resin and copper phthalocyanine crystals,
The X-ray diffraction of the copper phthalocyanine crystal shows a Bragg angle (2θ ± 0.20 °) in the range of 6.50 ° to 7.50 ° and a half width of 0.30 ° to 0.000. It has a diffraction peak of 34 ° or less. By making copper phthalocyanine into the specific crystal, a toner having good coloring power can be obtained.

  Copper phthalocyanine is a cyclic compound having isoindole, which is a heterocyclic compound in which a 6-membered benzene and a 5-membered pyrrole are bonded together sharing one side. In order to finely disperse copper phthalocyanine in the toner particles, the present inventors paid attention to the crystalline state of copper phthalocyanine. It was also found that by controlling the crystal state of copper phthalocyanine, a toner having good coloring power and appropriate chargeability can be obtained.

  The present inventors consider that the crystal state of copper phthalocyanine in the toner particles is represented by the half width of the main peak derived from the crystal of copper phthalocyanine obtained by X-ray diffraction analysis. The half width is the width of a peak at half the intensity of the diffraction peak. The half width of the diffraction peak correlates with the size of the copper phthalocyanine crystallite in the toner particles. Therefore, by setting the half-value width of the diffraction peak obtained by X-ray diffraction to the above range, the crystallites of copper phthalocyanine in the toner particles have an appropriate size, good coloring power, and appropriate chargeability. Toner can be obtained. The smaller the crystallite size, the broader the X-ray diffraction peak and the greater the half-value width. The half width of the diffraction peak of the present invention is 0.30 ° or more and 0.34 ° or less. Preferably, it is 0.31 ° or more and 0.33 ° or less. When the half-value width of the diffraction peak is less than 0.30 °, the crystal of copper phthalocyanine is in a large state, so that the dispersibility of copper phthalocyanine in the toner particles is lowered, and the coloring power and chargeability are lowered. There is a case. When the half-value width of the diffraction peak exceeds 0.34 °, the crystallinity of copper phthalocyanine in the toner particles may be lowered, and the color developability may be lowered.

  As an example of a method for controlling the crystal state of copper phthalocyanine in the toner particles, a strong crystal of copper phthalocyanine is doped with a compound that causes crystallites to change, and a mechanical share is added as an example. It is done.

  Copper phthalocyanine is a cyclic compound having crystallinity and having four isoindoles, which are heterocyclic compounds. Therefore, the interaction with a compound having crystallinity and an alicyclic compound having a cyclic structure is strong. For example, the crystalline state of copper phthalocyanine in the toner particles can be suitably controlled by including a crystalline polyester resin in the toner particles. Also, the crystalline state of copper phthalocyanine in the toner particles can be controlled to a suitable state by including a polymer in which the styrene acrylic polymer having a unit derived from a saturated alicyclic compound is graft-polymerized on the polyolefin. Is possible. Further, by adding a mechanical share, an interaction between a strong copper phthalocyanine crystal and a crystalline polyester resin or the polymer is likely to occur.

[Binder resin]
As the binder resin to be contained in the toner particles according to the present invention, for example,
Styrene homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and substituted products thereof;
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid Acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer, etc. Styrenic copolymer;
PVC;
Phenolic resin;
Naturally modified phenolic resin;
Natural resin-modified maleic resin;
acrylic resin;
Methacrylic resin;
Polyvinyl acetate;
Silicone resin;
Polyester resin;
Polyurethane resin;
Polyamide resin;
Furan resin;
Epoxy resin;
Xylene resin;
Polyvinyl butyral resin;
Terpene resin;
Coumarone-indene resin;
Examples include petroleum resins.

  Among these, a polyester resin is preferable from the viewpoint of improvement in coloring power and appropriate chargeability.

  Here, the polyester resin means a resin having a polyester unit in the resin chain.

  As a component for synthesizing a polyester unit, specifically, a divalent or higher valent alcohol monomer component, a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, a divalent or higher carboxylic acid ester, etc. And an acid monomer component.

Examples of the bivalent or higher alcohol monomer component include:
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenedio 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanete Trol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1 2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

  Among these, aromatic diols are preferable. In the alcohol monomer component used for the synthesis of the polyester resin, the aromatic diol is preferably contained in a proportion of 80 mol% or more.

Examples of acid monomer components such as divalent or higher carboxylic acid, divalent or higher carboxylic acid anhydride and divalent or higher carboxylic acid ester include:
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof;
Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof;
Succinic acid or anhydride thereof substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms;
Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Among these, terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and polyvalent carboxylic acids such as anhydrides thereof are preferable.

  The acid value of the polyester resin is preferably 20 mgKOH / g or less from the viewpoint of improving the dispersibility of copper phthalocyanine, improving the proper charging property of the toner, and improving the coloring power. More preferably, it is 15 mgKOH / g or less.

  The acid value of the polyester resin can be controlled by adjusting the type and amount of the monomer used for the synthesis of the polyester resin. Specifically, it can be controlled by adjusting the ratio of the alcohol monomer component and the acid monomer component during synthesis of the polyester resin and the molecular weight of the polyester resin. It can also be controlled by reacting a terminal alcohol with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

[Crystalline polyester resin]
The toner particles according to the present invention preferably contain a crystalline polyester resin.

  The content of the crystalline polyester resin in the toner particles is preferably 1 part by mass or more and 15 parts by mass or less, and preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles. More preferably.

  When the content of the crystalline polyester resin is in the above range, the coloring power of the toner is further improved and the chargeability becomes more appropriate. If content of crystalline polyester resin is 1 mass part or more, interaction with the crystal | crystallization of copper phthalocyanine will fully be obtained and coloring power will improve more. If the content of the crystalline polyester resin is 15 parts by mass or less, it becomes easy to finely disperse the crystalline polyester resin in the toner particles, the dispersibility of the copper phthalocyanine pigment is improved, the coloring power becomes better, the charging Sex becomes more moderate.

  A crystalline resin such as a crystalline polyester resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

  The crystalline polyester resin can be obtained by a polycondensation reaction between a divalent or higher carboxylic acid monomer component and a divalent or higher alcohol monomer component. Among them, a polyester resin that is a polycondensation product of an aliphatic diol and an aliphatic dicarboxylic acid has high crystallinity and easily interacts with copper phthalocyanine.

  Only one type of crystalline polyester resin may be used, or two or more types may be used in combination.

From the viewpoint of improvement in coloring power and appropriate chargeability, the crystalline polyester resin is
An aliphatic diol having 2 to 22 carbon atoms and / or a derivative thereof; and
A polycondensation product of an aliphatic dicarboxylic acid having 2 to 22 carbon atoms and / or a derivative thereof is preferable.

Among them, crystalline polyester resin is
An aliphatic diol having 6 to 12 carbon atoms and / or a derivative thereof; and
It is more preferably a polycondensation product of aliphatic dicarboxylic acids having 6 to 12 carbon atoms and / or derivatives thereof.

  The aliphatic diol having 2 to 22 carbon atoms is preferably a linear (preferably linear) aliphatic diol from the viewpoint of improving the coloring power of the toner and appropriate chargeability.

Examples of the aliphatic diol having 2 to 22 carbon atoms include:
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butadiene glycol, 1,5-pentanediol, neopentyl Glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol Etc. Among these,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. Straight chain aliphatic α, ω-diols are preferred.

  In the present invention, a derivative means one that can obtain a similar resin structure by the above condensation polymerization. Examples of the derivatives include those obtained by esterifying the diol.

  The alcohol monomer component for synthesizing the crystalline polyester resin preferably contains 50 mass% or more of the aliphatic diol having 2 to 22 carbon atoms and / or derivatives thereof, and is 70 mass% or more. More preferably it is included.

  Polyhydric alcohols other than the above aliphatic diols can also be used.

Among polyhydric alcohols, as diols other than the above aliphatic diols, for example,
Aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A;
Examples include 1,4-cyclohexanedimethanol.

Among polyhydric alcohols, trihydric or higher polyhydric alcohols include
Aromatic alcohols such as 1,3,5-trihydroxymethylbenzene;
Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, Examples include aliphatic alcohols such as trimethylolethane and trimethylolpropane.

  Furthermore, you may use monohydric alcohol.

As monovalent alcohol, for example,
Examples include n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol.

  The aliphatic dicarboxylic acid having 2 to 22 carbon atoms is preferably a linear (preferably linear) aliphatic dicarboxylic acid.

Examples of the aliphatic dicarboxylic acid having 2 to 22 carbon atoms include:
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid Acid, mesaconic acid, citraconic acid, itaconic acid and the like can be mentioned. Examples include hydrolyzed acid anhydrides or lower alkyl esters.

  In the present invention, a derivative means one that can obtain a similar resin structure by the above condensation polymerization. Examples of the derivatives include acid anhydrides of the dicarboxylic acid monomer component, and methyl esterified, ethyl esterified or acid chloride converted of the dicarboxylic acid monomer component.

  The carboxylic acid monomer component for synthesizing the crystalline polyester resin preferably contains 50% by mass or more of the above aliphatic dicarboxylic acid having 2 to 22 carbon atoms and / or derivatives thereof. % Is more preferable.

  Polyvalent carboxylic acids other than aliphatic dicarboxylic acids can also be used.

Among polyvalent carboxylic acids, examples of divalent carboxylic acids other than the aliphatic dicarboxylic acids include, for example,
Aromatic carboxylic acids such as isophthalic acid and terephthalic acid;
aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid;
And alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These acid anhydrides or lower alkyl esters are also included.

As other polyvalent carboxylic acid, as trivalent or higher polyvalent carboxylic acid, for example,
Aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid;
Examples thereof include aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane. These acid anhydrides or derivatives such as lower alkyl esters are also included.

  Further, a monovalent carboxylic acid may be used.

As monovalent carboxylic acid, for example,
Examples include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, and octanoic acid.

The crystalline polyester resin is, for example,
A method of esterifying a carboxylic acid monomer component and an alcohol monomer component;
After the transesterification reaction, it can be obtained by a method such as a method in which a condensation polymerization reaction is carried out according to a conventional method under reduced pressure or by introducing nitrogen gas.

  In the esterification or transesterification reaction, an esterification catalyst or a transesterification catalyst such as sulfuric acid, titanium butoxide, tin 2-ethylhexanoate, dibutyltin oxide, manganese acetate, and magnesium acetate is used as necessary. be able to.

  In the condensation polymerization reaction, for example, a polymerization catalyst such as titanium butoxide, tin 2-ethylhexanoate, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide is used. be able to.

  In the esterification or transesterification reaction or polycondensation reaction, in order to increase the strength of the obtained crystalline polyester resin, a method of charging all monomers at once may be used. In order to reduce the low molecular weight component, a method in which a divalent monomer is first reacted and then a trivalent or higher monomer is added and reacted may be used.

[wax]
The toner particles according to the present invention may contain a wax if necessary.

As a wax, for example,
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax;
Oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof;
Waxes based on fatty acid esters, such as carnauba wax;
Deoxidized part or all of fatty acid esters such as deacidified carnauba wax;
Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid;
Unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol;
Polyhydric alcohols such as sorbitol;
Esters of fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol;
Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide;
Saturated fatty acid bisamides such as methylene bis-stearic acid amide, ethylene bis-capric acid amide, ethylene bis-lauric acid amide, hexamethylene bis-stearic acid amide;
Unsaturated fatty acid amides such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl sebacic acid amide;
aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide;
Aliphatic metal salts (commonly called metal soaps) such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate;
Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid;
Partial esterified product of fatty acid such as behenic acid monoglyceride and polyhydric alcohol;
Examples include methyl ester compounds having a hydroxy group obtained by hydrogenation of vegetable oils.

  Among these waxes, Fischer-Tropsch wax is preferred from the viewpoint of toner coloring power and appropriate chargeability.

  The content of the wax in the toner particles is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles. More preferably, it is 3.0 to 12 parts by mass. Further, from the viewpoint of improving the coloring power of the toner, the peak temperature of the maximum endothermic peak existing in the range of 30 ° C. or more and 200 ° C. or less in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC). 50 ° C. or more and 110 ° C. or less is preferable. More preferably, it is 70 degreeC or more and 100 degrees C or less.

[Polymer having structure part derived from saturated alicyclic compound in polyolefin]
If necessary, the toner of the present invention may contain a polymer in which a styrene acrylic polymer having a structural site derived from a saturated alicyclic compound is graft-polymerized to a polyolefin. The polyolefin is preferably selected from the hydrocarbon waxes described above.

  Examples of the styrene acrylic polymer include those having a unit represented by the following formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a saturated alicyclic group.)
The saturated alicyclic group represented by R ^{2 in} the above formula (1) is preferably a saturated alicyclic hydrocarbon group from the viewpoint of enhancing the interaction with copper phthalocyanine. A saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms is more preferable, and a saturated alicyclic hydrocarbon group having 4 to 12 carbon atoms is more preferable.

  Examples of the saturated alicyclic hydrocarbon group include a cycloalkyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, and a spiro hydrocarbon group.

Examples of saturated alicyclic groups include:
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecanyl group, decahydro-2-naphthyl group, tricyclo [5.2.1.02, 6] A decan-8-yl group, a pentacyclopentadecanyl group, an isobornyl group, an adamantyl group, a dicyclopentanyl group, a tricyclopentanyl group, and the like.

  The saturated alicyclic group may have an alkyl group, a halogen atom, a carboxy group, a carbonyl group, a hydroxy group, or the like as a substituent. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improvement in coloring power and appropriate chargeability.

  Of the saturated alicyclic groups, a cycloalkyl group, a condensed polycyclic hydrocarbon group, and a bridged ring hydrocarbon group are preferable, a cycloalkyl group having 3 to 18 carbon atoms, a substituted or unsubstituted dicyclopentanyl group, A substituted or unsubstituted tricyclopentanyl group is more preferable. Furthermore, a cycloalkyl group having 4 to 12 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable from the viewpoint of improving the effect of interaction with copper phthalocyanine.

  When it has two or more substituents, the substituents may be the same or different.

  The styrene acrylic polymer may be a homopolymer of a vinyl monomer (a) having a structural site derived from a saturated alicyclic compound, or may be a copolymer of two or more vinyl monomers (a). It may be a copolymer with other monomer (b).

Examples of the vinyl monomer (a) include:
Cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, dihydrocyclopentadiethyl acrylate, Examples include dicyclopentanyl acrylate and dicyclopentanyl methacrylate.

Among these, from the viewpoint of improvement in coloring power and appropriate chargeability,
Cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, and cyclooctyl methacrylate are preferred.

As other monomer (b), for example,
Styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, m-methyl styrene, p-methoxy styrene, p-hydroxy styrene, p-acetoxy styrene, vinyl toluene, ethyl styrene, phenyl styrene, benzyl styrene;
Alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (the alkyl has 1 to 18 carbon atoms) Is preferred);
Vinyl ester monomers such as vinyl acetate;
Vinyl ether monomers such as vinyl methyl ether;
Halogen-containing vinyl monomers such as vinyl chloride;
Examples thereof include diene monomers such as butadiene and isobutylene. Of these, styrene and butyl acrylate are preferable.

[Colorant]
The toner particles according to the present invention contain the copper phthalocyanine crystals as a colorant.

  The content of the copper phthalocyanine crystals in the toner particles is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.

[Charge control agent]
The toner particles according to the present invention may contain a charge control agent as necessary. As the charge control agent, a metal compound of an aromatic carboxylic acid is preferable from the viewpoint of being colorless and having a high toner charging speed and being able to stably maintain a constant charge amount.

As a negative charge control agent, for example,
Salicylic acid metal compound,
Naphthoic acid metal compounds,
Dicarboxylic acid metal compounds,
A polymer compound having a sulfonic acid or carboxylic acid in the side chain;
A polymer compound having a sulfonate or a sulfonated ester in the side chain;
A polymer compound having a carboxylate or a carboxylic acid ester in the side chain;
Boron compounds,
Urea compounds,
Silicon compounds,
Examples include calix arene.

  The charge control agent may be added internally or externally to the toner particles.

  The content of the charge control agent in the toner particles is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.

[External additive]
If necessary, the toner of the present invention may contain an external additive from the viewpoint of improving fluidity and adjusting the triboelectric charge amount.

  As the external additive, for example, inorganic fine particles such as silicon oxide (silica), titanium oxide (titania), aluminum oxide (alumina), and strontium titanate are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

The specific surface area of the external additive is preferably 10 m ² / g or more and 50 m ² / g or less from the viewpoint of suppressing embedding of the external additive.

  The content of the external additive in the toner is preferably 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

  For mixing the toner particles and the external additive, for example, a mixer such as a Henschel mixer can be used.

  The toner of the present invention is preferably mixed with a magnetic carrier and used as a toner for a two-component developer from the viewpoint of obtaining a stable image over a long period of time.

Examples of magnetic carriers include:
Iron powder with oxidized surface,
Unoxidized iron powder,
Metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth,
Alloy particles of the above metals,
Oxide particles of the above metals,
Magnetic materials such as ferrite,
Magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state
Etc.

[Production method]
As a method for producing toner particles, it is preferable to employ a melt kneading method from the viewpoint of controlling the crystallinity of copper phthalocyanine in the toner particles and improving the dispersibility.

  The melt-kneading method is a step of obtaining a melt-kneaded product by melting and kneading a mixture containing a binder resin and a colorant (in the present invention, copper phthalocyanine) and, if necessary, a wax and a wax dispersant. (Hereinafter, also simply referred to as “melt-kneading step”).

  When the toner particles are manufactured through a melt-kneading process, the crystallinity of copper phthalocyanine changes depending on heat and shear.

  Hereinafter, a procedure for producing toner particles using the melt-kneading method will be described.

In the raw material mixing step, as a material constituting the toner particles, for example, a binder resin and a colorant (copper phthalocyanine), and, if necessary, components such as a wax and a charge control agent are weighed and blended in predetermined amounts. Mix. As a mixing device, for example,
Double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauter mixer, Mechano Hybrid (manufactured by Nippon Coke Industries Co., Ltd.)
Etc.

Next, the mixed material is melt-kneaded to disperse a colorant (copper phthalocyanine) or the like in the binder 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 are the mainstream. For example,
KTK type twin screw extruder (manufactured by Kobe Steel)
TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.),
PCM kneader (made by Ikegai Co., Ltd.),
2-axis extruder (manufactured by Kay C. K.)
Ko Kneader (Bus)
Needex (Nippon Coke Kogyo Co., Ltd.)
Etc.

  The kneaded material obtained by melt-kneading may be rolled with two rolls or the like, or cooled with water or the like in the cooling step.

  The kneader used in the examples described later is a same-direction biaxial extruder.

  The biaxial extruder is a kneader in which two kneading shafts called paddles pass through a barrel that is a heating cylinder that keeps the temperature constant. An example of a biaxial extruder is shown in FIG.

  The raw material mixture is supplied from one end of the kneading shaft, heated to be in a molten state, kneaded by rotation of the kneading shaft, and extruded from the other end. A vent hole mainly for deaeration may be installed on the way.

  For the cross section of the kneading shaft, a propeller-like or triangular one is adopted. It is set with a phase shift so that one tip always rotates to rub the other. With this structure, it has a self-cleaning action to feed the kneaded material forward while suppressing the kneaded material from adhering to the kneading shaft and barrel wall.

  The rotation directions of the two kneading shafts are preferably the same direction. An appropriate shear force can be applied by rotating the kneading shaft in the same direction. When an appropriate shear force can be applied, copper phthalocyanine is uniformly dispersed, and crystal growth of copper phthalocyanine can be suppressed. If the rotation of the kneading shaft is in a different direction, the shearing force is too strong and self-heating may occur during kneading. When self-heating occurs, copper phthalocyanine grows and the coloring power may decrease.

  The kneading shaft is roughly divided into two types, one being a feed screw portion and the other being a kneading portion. A screw part has the function to send a kneaded material forward, heating. When the viscosity of the kneaded material in the cylinder is high, the kneaded material is kneaded by a shearing force caused by friction between the wall of the screw portion and the kneaded material, but when the viscosity is low, the material is hardly kneaded. The kneading part has little effect of feeding the kneaded material forward, and the kneaded material stays and fills up.

  When producing the toner of the present invention, the difference (Tb−Ta) between the barrel set temperature (Ta) of the kneading part and the temperature (Tb) of the kneaded product is preferably 30 ° C. or more and 90 ° C. or less, and 40 ° C. More preferably, the temperature is 70 ° C. or lower. The temperature of the kneaded product can be controlled by the set temperature of the barrel (C0, C1, C2, C3 = Ta, C4 in FIG. 1), the number of rotations of the kneading shaft, and the feed (supply) amount. When Tb-Ta (° C.) is less than 30 ° C., the effect of compression and stretching accompanying rotation of the kneading shaft performed in the kneading part is small. Therefore, the share concerning the crystal | crystallization of copper phthalocyanine becomes weak. When Tb-Ta (° C.) exceeds 90 ° C., the share of copper phthalocyanine crystals is too strong and the crystals are liable to collapse. If the crystals are broken, the color developability of the toner may be reduced.

  The cooled product of the kneaded product is pulverized to a desired particle size in the pulverization step. In the pulverization step, the material is roughly pulverized by a pulverizer and further pulverized by a fine pulverizer. Examples of the pulverizer that performs coarse pulverization include a crusher, a hammer mill, and a feather mill. Examples of the fine pulverizer that performs fine pulverization include a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nissin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industry Co., Ltd.), and an air jet. Examples include a fine pulverizer.

Thereafter, classification is performed using a classifier or a sieving machine as necessary to obtain toner particles. Examples of classifiers and sieving machines include:
Inertia classification elbow jet (manufactured by Nippon Steel Mining Co., Ltd.),
Centrifugal force classification turboplex (manufactured by Hosokawa Micron Corporation),
TSP separator (manufactured by Hosokawa Micron Corporation),
Faculty (manufactured by Hosokawa Micron Corporation)
Etc.

  Thereafter, if necessary, for example, in order to impart fluidity to the toner or to appropriately charge the toner, external additives such as inorganic fine particles and resin particles are added and mixed (externally added) with the toner particles. Thus, a toner is obtained. As a mixing apparatus, it can carry out with the mixing apparatus which has the rotary body which has a stirring member, and the main body casing provided with the stirring member and the clearance gap.

As a mixing device, for example,
Henschel mixer (Mitsui Mine Co., Ltd.),
Super mixer (manufactured by Kawata Co., Ltd.), ribocorn (manufactured by Okawara Seisakusho Co., Ltd.),
Nauter mixer, turbulizer, cyclomix, nobilta (manufactured by Hosokawa Micron Corporation), spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.),
Ladige mixer (manufactured by Matsubo)
Etc. In particular, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is suitable for uniformly mixing the external additive and the toner particles and loosening the aggregate of the external additive.

  Examples of the mixing conditions include a processing amount, a stirring shaft rotation speed, a stirring time, a stirring blade shape, and a tank temperature.

  In the case where coarse aggregates of additives are present in the obtained toner in a free state, a sieving machine or the like may be used as necessary.

  Hereinafter, a method for measuring various physical properties of the toner and raw materials in the present invention will be described.

[Measurement method of peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) of resin]
The peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) as follows.

  First, a sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter (trade name: Maesho Disc, manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.

Apparatus: HLC8120GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample,
Standard polystyrene resin (trade names: TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, manufactured by Tosoh Corporation)
Use a molecular weight calibration curve created using.

[Measurement method of softening point of resin]
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer (trade name: flow characteristic evaluation device, flow tester CFT-500D, manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus flow tester CFT-500D” is the softening point.

  The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of resin is compressed for about 60 seconds at about 10 MPa using a tablet molding compressor (trade name: NT-100H, manufactured by NP System Co., Ltd.) in an environment of 25 ° C. 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 Starting temperature: 40 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min 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: 1.0mm

[Measurement method of acid value of resin]
The acid value is the mass [mg] of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K0070-1992. Specifically, it measures according to the following procedures.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), 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% by volume) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and left for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The potassium hydroxide solution was prepared by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and neutralizing the potassium hydroxide required for neutralization. Determine from the amount of solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K8001-1998 is used.

(2) Operation (A) Main test 2.0 g of a 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 described 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 potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

[Measurement method of hydroxyl value of resin]
The hydroxyl value is the mass [mg] of potassium hydroxide required to neutralize acetic acid bonded to a hydroxy group (hydroxyl group) when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K0070-1992. Specifically, it measures according to the following procedures.

(1) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 mL volumetric flask, pyridine is added to make a total volume of 100 mL, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution.

  Dissolve 35 g of special grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and left for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. Factor of the potassium hydroxide solution is as follows. 25 mL of 0.5 mol / L hydrochloric acid is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution is added, titrated with the potassium hydroxide solution, and the potassium hydroxide required for neutralization. Determine from the amount of solution. As the 0.5 mol / L hydrochloric acid, one prepared according to JIS K8001-1998 is used.

(2) Operation (A) Main test A 1.0 g sample of the pulverized binder resin is precisely weighed into a 200 mL round bottom flask, and 5.0 mL of the acetylating reagent is accurately added thereto using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  Place a small funnel on the flask mouth and immerse the bottom of the flask about 1 cm in a glycerin bath at about 97 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. In addition, the flask is again heated in a glycerin bath for 10 minutes to fully hydrolyze. After cooling, wash the funnel and flask walls with 5 mL of ethyl alcohol.

  Add several drops of the phenolphthalein solution as an indicator and titrate with 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 similar to the above operation is performed except that no binder resin sample is used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Factor of solution, S: sample (g), D: acid value of binder resin (mgKOH / g).

[Measurement of maximum endothermic peak of wax and crystalline polyester resin]
The peak temperature of the maximum endothermic peak of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter (trade name: Q1000, manufactured by TA Instruments). 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 5 mg of a sample is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as a reference, and the rate of temperature rise is between a measurement temperature range of 30 ° C. and 200 ° C. The measurement is performed at 10 ° 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 temperature showing the maximum endothermic peak of the DSC curve in the range of 30 ° C. or more and 200 ° C. or less in the second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.

[Measurement method of X-ray diffraction]
The X-ray diffraction measurement uses a measuring device (trade name: RINT-TTRII, manufactured by Rigaku Corporation), and control software and analysis software attached to the device.

The measurement conditions are as follows.
X-ray: Cu / 50kV / 300mA
Goniometer: Rotor horizontal goniometer (TTR-2)
Attachment: Standard sample holder Divergence slit: Release Divergence length limit slit: 10.00mm
Scattering slit: Opening Light receiving slit: Opening Counter: Scintillation counter Scanning mode: Continuous Scanning speed: 4.0000 ° / min.
Sampling width: 0.0200 °
Scanning axis: 2θ / θ
Scanning range: 10.0000 ° to 40.0000 °

  Subsequently, toner is set on the sample plate and measurement is started. For CuKα characteristic X-rays, measurement is performed in a Bragg angle (2θ ± 0.20 °) range of 3.00 ° to 35.00 °. From the obtained spectrum, the half width of the spectrum at 2θ of 6.50 ° or more and 7.50 ° or less was used as an index of crystallinity of copper phthalocyanine in the toner.

  Hereinafter, the present invention will be specifically described based on examples.

[Production Example of Binder Resin 1]
76.9 parts by mass (0.167 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane,
24.1 parts by mass (0.145 mol) of terephthalic acid,
8.0 parts by mass of adipic acid (0.054 mol), and
0.5 parts by mass of titanium tetrabutoxide was placed in a 4 L 4-neck flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater.

  Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step).

  Thereafter, 1.2 parts by mass (0.006 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 1 was obtained.

  The acid value of the binder resin 1 was 5 mgKOH / g, and the hydroxyl value was 65 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) of 8,000, a number average molecular weight (Mn) of 3,500, and a peak molecular weight (Mp) of 5,700. The softening point was 90 ° C.

[Example of production of binder resin 2]
71.3 parts by mass (0.155 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane,
24.1 parts by mass (0.145 mol) of terephthalic acid, and
0.6 parts by mass of titanium tetrabutoxide was placed in a 4 L 4-neck flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached, and placed in a mantle heater.

  Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (first reaction step).

  Thereafter, 5.8 parts by mass (0.030 mol%) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step), whereby a binder resin 2 was obtained.

  The acid value of the binder resin 2 was 15 mgKOH / g, and the hydroxyl value was 7 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) of 200,000, a number average molecular weight (Mn) of 5,000, and a peak molecular weight (Mp) of 10,000. The softening point was 130 ° C.

[Production Example of Crystalline Polyester Resin 1]
33.9 parts by mass of hexanediol (0.29 mol, 100.0 mol% with respect to the total number of moles of polyhydric alcohol), and
66.1 parts by mass of dodecanedioic acid (0.29 mol, 100.0 mol% with respect to the total number of polycarboxylic acids)
Were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube and a thermocouple.

  Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.

  Thereafter, 0.5 parts by mass of tin 2-ethylhexanoate was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining at 200 ° C.

  Thereafter, the inside of the reaction vessel was depressurized to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain a crystalline polyester resin 1.

[Production Example of Crystalline Polyester Resins 2 and 3]
In the production example of the crystalline polyester resin 1, the crystalline polyester resins 2 and 3 are the same as the production example of the crystalline polyester resin 1 except that the aliphatic diol and the aliphatic dicarboxylic acid are changed as shown in Table 1. Manufactured.

[Production Example of Polymer 1]
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 300 parts of xylene and 10 parts of hydrocarbon wax (softening point: 90 ° C.) were added to dissolve the hydrocarbon wax. After nitrogen substitution, a mixed solution of 68.9 parts of styrene, 7.65 parts of α-methylstyrene, 13.5 parts of cyclohexyl methacrylate and 250 parts of xylene was dropped at 180 ° C. for 3 hours to polymerize them. Furthermore, it was kept at this temperature for 30 minutes. Next, the solvent was removed to obtain a polymer 1.

[Production Example of Polymers 2 to 4]
In the production example of polymer 1, polymers 2 to 4 were produced in the same manner as in the production example of polymer 1 except that the raw materials shown in Table 2 were changed.

[Production Example of Toner 1]
70.0 parts by mass of binder resin 1
Binder resin 2 30.0 parts by mass,
7.5 parts by mass of crystalline polyester resin 1
Fischer-Tropsch wax (peak temperature of maximum endothermic peak: 90 ° C.) 5.0 parts by mass,
5.0 parts by weight of polymer 1 and
C. I. Pigment Blue 15: 3 5.0 parts by mass were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 seconds ⁻¹ and a rotation time of 5 minutes. Then, melt kneading conditions 1 in Table 3 (kneading shaft set temperature C0: 30 ° C, C1: 70 ° C, C2: 90 ° C, C3 = barrel setting temperature Ta: 90 ° C of kneading part, C4: 90 ° C, The kneading shaft was kneaded with a twin-screw extruder (trade name: PCM-70 type, manufactured by Ikegai Co., Ltd.) set so that the rotation speed of the kneading shaft was 400 rpm and the supply amount was 20 kg / hour. The temperature Tb of the kneaded material was directly measured using a handy type thermometer (trade name: HA-200E, manufactured by Anritsu Keiki Co., Ltd.). The temperature Tb of the obtained kneaded material was 150 ° C.

  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 crushed material was finely pulverized with a mechanical pulverizer (trade name: T-250, manufactured by Turbo Kogyo Co., Ltd.).

Furthermore, classification was performed using a rotary classifier (trade name: 200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating condition of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) was set to 50.0 sec- ¹ for the classifying rotor speed.

The obtained toner particles had a weight average particle diameter (D4) of 6.2 μm.
To 100 parts by mass of the obtained toner particles, 0.8 part by mass of hydrophobic silica fine particles having a number average particle diameter of 10 nm of primary particles surface-treated with 20% by mass of hexamethyldisilazane was added. Then, using a Henschel mixer (trade name: FM-75 type, manufactured by Mitsui Mining Co., Ltd.), these were mixed under the conditions of a rotation speed of 30 seconds- ¹ and a rotation time of 10 minutes, to obtain toner 1.

[Production Examples of Toners 2 to 18]
As shown in Tables 3 and 4, the toners 2 to 18 were prepared in the same manner as in the production example of the toner 1 except that the melt-kneading conditions, the types of the crystalline polyester resin and the polymer, and the respective amounts used were changed. Manufactured.

[Production Example of Magnetic Core Particle 1]
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 parts by mass were weighed. Then, these were put in a dry vibration mill using stainless steel beads having a diameter of 1/8 inch and pulverized for 5 hours and mixed.

-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve having an opening of 3 mm. Next, fine powder was removed with a vibrating sieve having an aperture of 0.5 mm. Thereafter, using a burner-type firing furnace, firing was performed at a temperature of 1000 ° C. for 4 hours in a nitrogen atmosphere (oxygen concentration 0.01% by volume) to prepare calcined ferrite.

  The composition of the obtained calcined ferrite is as follows.

(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (grinding step):
It grind | pulverized to about 0.3 mm with the crusher. Thereafter, using zirconia beads having a diameter of 1/8 inch, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite, and the mixture was pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to 100 parts by mass of calcined ferrite. Then, it was granulated into spherical particles with a spray dryer (Okawara Chemical Co., Ltd.). After adjusting the particle size of the obtained particles, the mixture was heated at 650 ° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and the binder.

-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours. Then, it baked at 1150 degreeC for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.

-Process 6 (screening process):
Aggregated particles were crushed. Thereafter, the low magnetic force product was cut by magnetic separation, and the coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain a magnetic core particle 1 having a volume distribution standard 50% particle size (D50) of 37.0 μm. .

[Preparation of coating resin 1]
26.8 parts by weight of cyclohexyl methacrylate monomer,
0.2 parts by weight of methyl methacrylate monomer,
8.4 parts by mass of a methyl methacrylate macromonomer (a macromonomer having a methacryloyl group at one end and a weight average molecular weight of 5000)
31.3 parts by mass of toluene,
31.3 parts by weight of methyl ethyl ketone, and
Out of 2.0 parts by mass of azobisisobutyronitrile, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, methyl ethyl ketone were added to a four-neck equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device. Added to separable flask. And after introducing nitrogen gas and making it nitrogen atmosphere, it heated to 80 degreeC, azobisisobutyronitrile was added, and it recirculate | refluxed for 5 hours, and polymerized these.

  Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration. Thereafter, the coating resin 1 was obtained by vacuum drying. 30 parts by mass of the obtained coating resin 1 was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

[Preparation of coating resin solution 1]
Polymer solution 1 (resin solid content concentration 30%) 33.3 parts by mass Toluene 66.4 parts by mass Carbon black (primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 mL / 100 g) (trade name) : Regal 330, manufactured by Cabot Corporation) 0.3 parts by mass were dispersed for 1 hour with a paint shaker using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

[Example of manufacturing magnetic carrier 1]
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the filled core particles 1. After the addition, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm, and the solvent was volatilized above a certain level (80% by mass). Thereafter, the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling.

  The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier. 1 was obtained.

[Examples 1 to 15 and Comparative Examples 1 to 3]
As the concentration of toner is 9 wt%, V-type mixer (trade name: V-10 type, Inc. Tokuju Seisakusho) using a toner 1 and 5 minutes 0.5 sec ^-1 and rotation time A magnetic carrier 1 was mixed to obtain a two-component developer 1.

  Further, the toner and magnetic carrier to be combined were changed as shown in Table 5 to obtain two-component developers 2 to 18.

  The following evaluation was performed using the two-component developers 1 to 18 as the two-component developers of Examples 1 to 15 and Comparative Examples 1 to 3.

  Table 6 shows the evaluation results of Examples 1 to 15 and Comparative Examples 1 to 3.

(Evaluation method of toner coloring power)
Evaluation was performed by using a modified machine of a full-color copying machine (trade name: image RUNNER ADVANCE C5255) manufactured by Canon Inc. as the image forming apparatus, and supplying the two-component developer 1 to the developing unit of the cyan station.

The evaluation environment was a normal temperature and normal humidity environment (temperature 23 ° C., relative humidity 50%). The evaluation paper used was a plain paper for copying (trade name: GFC-081, A4 paper, basis weight 81.4 g / m ² , sold by Canon Marketing Japan Inc.).

  First, in the evaluation environment (normal temperature and humidity environment), the amount of toner applied on the paper was changed, and the relationship between the image density and the amount of toner applied on the paper was examined.

  Next, the image density of the FFH image (solid portion) was adjusted to 1.40, and the amount of applied toner when the image density became 1.40 was obtained.

  The FFH image is a value in which 256 gradations are displayed in hexadecimal, and 00H is the first gradation (white background), and FFH is the 256th gradation (solid part).

  The image density was measured using an X-Rite color reflection densitometer (trade name: 500 series: manufactured by X-Rite).

From the toner applied amount (mg / cm ² ), the coloring power of the toner was evaluated according to the following criteria. The evaluation results are shown in Table 6.

(Evaluation criteria)
A: Less than 0.35 B: 0.35 or more and less than 0.50 C: 0.50 or more and less than 0.65 D: 0.65 or more

(Method for evaluating fog on non-image areas)
As the image forming apparatus, a remodeling machine similar to the above was used, and the two-component developer 1 was put into the developing unit of the cyan station and evaluated.

  The evaluation environment was a normal temperature and normal humidity environment (temperature 23 ° C., relative humidity 50%) and a high temperature and high humidity environment (temperature 30 ° C., relative humidity 80%). As the evaluation paper, the same plain paper for copying as described above was used.

  The fog on the white background after the durability test in each environment was measured.

  The average reflectance Dr (%) of the evaluation paper before image output was measured with a reflectometer (trade name: REFECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku).

The reflectance Ds (%) of the 00H image portion (white background portion) after the durability test (50000th sheet) was measured. The fog value (%) was calculated from the obtained Dr and Ds using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog value (%) = Dr (%) − Ds (%)
The evaluation results are shown in Table 6.

(Evaluation criteria)
A: Less than 0.5% (fogging cannot be confirmed visually)
B: 0.5% or more and less than 1.0% (The fog value is larger than A, but the fog cannot be visually confirmed.)
C: 1.0% or more and less than 2.0% (Fog can be confirmed only slightly by visual observation.)
D: 2.0% or more (fogging can be confirmed visually)

Claims (6)

A toner having toner particles containing a binder resin and crystals of copper phthalocyanine,
The X-ray diffraction of the copper phthalocyanine crystal shows a Bragg angle (2θ ± 0.20 °) in the range of 6.50 ° to 7.50 ° and a half width of 0.30 ° to 0.000. A toner having a diffraction peak of 34 ° or less.   2. The toner according to claim 1, wherein the content of the copper phthalocyanine crystals in the toner particles is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.   The toner according to claim 1, wherein the binder resin contains a crystalline polyester resin. The crystalline polyester resin is
An aliphatic diol having 6 to 12 carbon atoms, and
The toner according to claim 1, which is a polycondensation product of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms.   The toner according to claim 1, wherein the toner particles further contain a polymer in which a styrene acrylic polymer having a unit derived from a saturated alicyclic compound is graft-polymerized to a polyolefin. A toner production method for producing the toner according to claim 1,
The production method has a melt-kneading step of melt-kneading the mixture containing the binder resin and the copper phthalocyanine by a biaxial extruder having a kneading shaft,
In the melt-kneading step, when the barrel setting temperature of the kneading part of the kneading shaft is Ta (° C.) and the temperature of the kneaded product obtained by the melt-kneading step is Tb (° C.), Ta and Tb are 30 ≦ Tb−Ta ≦ 90 is satisfied.

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