JP6971633B2 - Toner and toner manufacturing method - Google Patents

Description

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

Particularly important properties for toners are moderate chargeability and good tinting strength, and they are stable over a long period of time. For that 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 preferably used as a colorant for cyan toner. Copper phthalocyanines have excellent performance in terms of cost and light resistance.

However, copper phthalocyanine has strong crystallinity and tends to have a strong cohesive force between particles of copper phthalocyanine crystals, so that dispersion in a medium such as an organic solvent and a molten resin tends to be insufficient. When the dispersibility of the particles of the copper phthalocyanine crystal is insufficient, it tends to cause a decrease in the coloring power of the toner and a decrease in the chargeability.

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

Patent Document 2 discloses a technique of incorporating a copper phthalocyanine derivative in toner particles to improve pigment dispersibility in toner particles.

In Patent Documents 3 and 4, as a technique that does not use a pigment dispersant, a method of mixing a pigment with a part of a binder resin to perform a masterbatch step, or using the pigment in a paste state containing water is used. A method of suppressing the growth of particles is disclosed.

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

Japanese Patent Application Laid-Open No. 03-136462 Japanese Unexamined Patent Publication No. 2004-341397 Japanese Unexamined Patent Publication No. 06-130724 Japanese Unexamined Patent Publication No. 08-314180

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

The present invention is a toner having toner particles containing crystals of a binder resin and copper phthalocyanine.
The crystals of the copper phthalocyanine have a half-value width of 0.30 ° or more and 0. It is a toner characterized by having a diffraction peak of 34 ° or less.

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

It is a figure which shows an example of the two-screw extruder used in this invention.

The toner of the present invention is a toner having toner particles containing crystals of a binder resin and copper phthalocyanine.
The crystals of the copper phthalocyanine have a half-value width of 0.30 ° or more and 0. It is characterized by having a diffraction peak of 34 ° or less. By forming the copper phthalocyanine into the above-mentioned specific crystals, a toner having good coloring power can be obtained.

Copper phthalocyanine is a cyclic compound having isoindole, which is a heterocyclic compound in which 6-membered benzene and 5-membered pyrrole are bonded on one side. In order to finely disperse the copper phthalocyanine in the toner particles, the present inventors focused on the crystalline state of the copper phthalocyanine. Then, they have found that by controlling the crystal state of copper phthalocyanine, a toner having a good coloring power and an 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 crystals of copper phthalocyanine obtained by X-ray diffraction analysis. The full width at half maximum is the width of the peak at half the intensity of the diffraction peak intensity. The half width of the diffraction peak correlates with the size of the crystallites of copper phthalocyanine in the toner particles. Therefore, by setting the half width of the diffraction peak obtained by X-ray diffraction within the above range, the crystallites of copper phthalocyanine in the toner particles become an appropriate size, the coloring power is good, and the toner particles have an appropriate chargeability. Toner can be obtained. The smaller the crystallite size, the broader the X-ray diffraction peak and the larger the half width. The half width of the diffraction peak of the present invention is 0.30 ° or more and 0.34 ° or less. It is preferably 0.31 ° or more and 0.33 ° or less. When the half width of the diffraction peak is less than 0.30 °, the crystals of copper phthalocyanine are 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. In some cases. When the half width of the diffraction peak exceeds 0.34 °, the crystallinity of the copper phthalocyanine in the toner particles may decrease, and the color development property may decrease.

One example of a method for controlling the crystal state of copper phthalocyanine in toner particles is to dope a strong crystal of copper phthalocyanine with a compound that causes a change in crystallites, and further add a mechanical share. Be done.

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

[Bundling resin]
Examples of the binder resin contained in the toner particles according to the present invention include, for example.
Styrene-based homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions;
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacryl Methyl acid acid copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-inden copolymer, etc. Styrene-based copolymer;
PVC;
Phenol resin;
Intrinsically disordered phenolic resin;
Natural resin modified maleic acid 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;
Kumaron-Inden resin;
Petroleum-based resins and the like can be mentioned.

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

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

Specific examples of the components for synthesizing the polyester unit include a divalent or higher alcohol monomer component, a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a divalent or higher carboxylic acid ester. Examples include acid monomer components.

Examples of the divalent or higher alcohol monomer component include, for example.
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 adduct 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-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Tetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5- Examples thereof include pentantriol, 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 the acid monomer component such as a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a divalent or higher carboxylic acid ester include, for example.
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides;
Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides;
Succinic acid or anhydrate thereof substituted with an alkyl group or an 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, polyvalent carboxylic acids such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their anhydrides 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, appropriate chargeability 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 blending amount of the monomer used for synthesizing the polyester resin. Specifically, it can be controlled by adjusting the ratio of the alcohol monomer component and the acid monomer component at the time of synthesizing the polyester resin and the molecular weight of the polyester resin. It can also be controlled by reacting the terminal alcohol with a polyhydric acid monomer (for example, trimellitic acid) after ester polycondensation.

[Crystalline polyester resin]
It is preferable that the toner particles according to the present invention 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 with respect to 100 parts by mass of the binder resin in the toner particles, and is preferably 2 parts by mass or more and 10 parts by mass or less. It is more preferable to have.

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. When the content of the crystalline polyester resin is 1 part by mass or more, the interaction with the crystals of copper phthalocyanine can be sufficiently obtained, and the coloring power is further improved. When 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 also improved, the coloring power is improved, and the charge is charged. The 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, the polyester resin, which is a polycondensation polymer of an aliphatic diol and an aliphatic dicarboxylic acid, has a high crystallinity and easily interacts with copper phthalocyanine.

As the crystalline polyester resin, only one kind may be used, or two or more kinds may be used in combination.

Crystalline polyester resin is used from the viewpoint of improving coloring power and appropriate chargeability.
Aliphatic diols having 2 or more and 22 or less carbon atoms and / or derivatives thereof, and
It is preferably a polycondensation polymer of an aliphatic dicarboxylic acid having 2 or more carbon atoms and 22 or less carbon atoms and / or a derivative thereof.

Among them, crystalline polyester resin is
Aliphatic diols having 6 or more and 12 or less carbon atoms and / or derivatives thereof, and
More preferably, it is a polycondensate of an aliphatic dicarboxylic acid having 6 or more carbon atoms and 12 or less carbon atoms and / or a derivative thereof.

As the aliphatic diol having 2 or more carbon atoms and 22 or less carbon atoms, a chain-like (preferably linear) aliphatic diol is preferable from the viewpoint of improving the coloring power of the toner and appropriate chargeability.

Examples of the aliphatic diol having 2 or more and 22 or less carbon atoms include, for example.
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-octanediyl, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol And so on. Among these,
1,6-Hexanediol, 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. Linear aliphatic α and ω-diols are preferable.

In the present invention, the derivative means a derivative obtained by the above-mentioned polycondensation to obtain a similar resin structure. Examples of the derivative include those obtained by esterifying the above diol.

The alcohol monomer component for synthesizing the crystalline polyester resin preferably contains 50% by mass or more of the above-mentioned aliphatic diol having 2 or more and 22 or less carbon atoms and / or a derivative thereof, and 70% by mass or more. It is more preferable that it is contained.

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

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

Of the polyhydric alcohols, the trihydric or higher polyhydric alcohols are
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 thereof include aliphatic alcohols such as trimethylolethane and trimethylolpropane.

Further, monohydric alcohol may be used.

As a monohydric alcohol, for example,
Examples thereof include n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol and the like.

The aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms is preferably a chain (preferably linear) aliphatic dicarboxylic acid.

Examples of the aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms include, for example.
Shuic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, maleic acid, fumal Acids, mesaconic acid, citraconic acid, itaconic acid and the like can be mentioned. Hydrolyzed ones of these acid anhydrides or lower alkyl esters are also mentioned.

In the present invention, the derivative means a derivative obtained by the above-mentioned polycondensation to obtain a similar resin structure. Examples of the derivative include an acid anhydride of the dicarboxylic acid monomer component, and a methyl esterified, ethyl esterified or acid chloride-ized product 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-mentioned aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms and / or a derivative thereof, and 70% by mass. It is more preferable that it is contained in% or more.

A polyvalent carboxylic acid other than the aliphatic dicarboxylic acid can also be used.

Among the polyvalent carboxylic acids, examples of the divalent carboxylic acid other than the above aliphatic dicarboxylic acid 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;
Examples thereof include alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. Examples thereof include these acid anhydrides or lower alkyl esters.

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

Further, a monovalent carboxylic acid may be used.

Examples of the monovalent carboxylic acid include, for example.
Examples thereof 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 of reducing the pressure or introducing nitrogen gas and carrying out a polycondensation reaction according to a conventional method.

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

Further, in the above-mentioned 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 and the like 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 the monomers at once may be used. Further, in order to reduce the number of low molecular weight components, a method may be used in which a divalent monomer is first reacted and then a trivalent or higher-valent monomer is added to cause the reaction.

[wax]
If necessary, the toner particles according to the present invention may contain wax.

As wax, for example
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fishertroph wax;
Hydrocarbon wax oxides or block copolymers thereof, such as polyethylene oxide wax;
Waxes mainly composed of fatty acid esters such as carnauba wax;
Deoxidized Part or all of fatty acid esters, such as carnauba wax;
Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid;
Unsaturated fatty acids such as brushzic acid, eleostearic acid, and varinaphosphoric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol, and mericyl alcohol;
Multivalent alcohols such as sorbitol;
Esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and mericyl alcohol;
Fatty acid amides such as linoleic acid amides, oleic acid amides, and lauric acid amides;
Saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide;
Unsaturated fatty acid amides such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipic acid amides, N, N'diorail sevacinic acid amides;
Aromatic bisamides such as m-xylene bisstearic acid amide, N, N'distearyl isophthalic acid amide;
Aliper metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally called metal soap);
Waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid;
Partial esterification of fatty acids such as behenic acid monoglyceride and polyhydric alcohols;
Examples thereof include methyl ester compounds having a hydroxy group obtained by hydrogenation of vegetable oils and fats.

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

The wax content 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 parts by mass or more and 12 parts by mass or less. 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 higher and 200 ° C. or lower is set in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry device (DSC). , 50 ° C. or higher and 110 ° C. or lower is preferable. More preferably, it is 70 ° C. or higher and 100 ° C. or lower.

[Polymer having a structural moiety derived from a 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 moiety derived from a saturated alicyclic compound is graft-polymerized on a polyolefin. The polyolefin is preferably selected from the above-mentioned hydrocarbon waxes.

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

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

Examples of the saturated alicyclic group include, for example.
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecanyl group, decahydro-2-naphthyl group, tricyclo [5.2.1.102, 6] Examples thereof include a decane-8-yl group, a pentacyclopentadecanyl group, an isobornyl group, an adamantyl group, a dicyclopentanyl group and a tricyclopentanyl group.

Further, 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 or more carbon atoms and 4 or less carbon atoms is preferable from the viewpoint of improving coloring power and appropriate chargeability.

Among 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, and the like. Substituted or unsubstituted tricyclopentanyl groups are more preferred. Further, a cycloalkyl group having 4 or more and 12 or less carbon atoms is preferable, and a cycloalkyl group having 6 or more and 10 or less carbon atoms is more preferable from the viewpoint of improving the effect of interaction with copper phthalocyanine.

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

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

Examples of the vinyl-based monomer (a) include, for example.
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 thereof include dicyclopentanyl acrylate and dicyclopentanyl methacrylate.

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

Examples of the other monomer (b) include, for example.
Styrene-based monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene;
Alkyl ester of unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (the number of carbon atoms of the alkyl is 1 or more and 18 or less). Is preferable.);
Vinyl ester-based monomers such as vinyl acetate;
Vinyl ether-based monomers such as vinyl methyl ether;
Halogen element-containing vinyl-based monomers such as vinyl chloride;
Examples thereof include diene-based 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 above-mentioned crystals of copper phthalocyanine 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, if necessary. As the charge control agent, a metal compound of an aromatic carboxylic acid is preferable from the viewpoint of being colorless, having a high charging speed of the toner, and being able to stably maintain a constant charge amount.

As a negative charge control agent, for example,
Salicylic acid metal compound,
Naftoate metal compounds,
Dicarboxylic acid metal compound,
Polymeric compounds with sulfonic acid or carboxylic acid in the side chain,
Polymer compounds with sulfonates or sulfonic acid esters in their side chains,
Polymeric compounds with carboxylates or carboxylic acid esters in their side chains,
Boron compound,
Urea compound,
Silicon compound,
Calixarene and the like.

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 agent]
If necessary, the toner of the present invention may contain an external additive from the viewpoint of improving the 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 the embedding of the external additive.

The content of the external additive in the toner is preferably 0.1 part 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.

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

As a magnetic carrier, for example,
Iron powder with oxidized surface,
Unoxidized iron powder,
Metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earths,
Alloy particles of the above metals,
Oxide particles of the above metal,
Magnetic material such as ferrite,
A 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.
And so on.

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

The melt-kneading method is a step of melting and kneading a mixture containing a binder resin, a colorant (in the case of the present invention, copper phthalocyanine), and, if necessary, a wax, a wax dispersant, etc. to obtain a melt-kneaded product. This is a method for producing toner particles, which comprises (hereinafter, also simply referred to as “melting and kneading step”).

As the toner particles are produced through a melt-kneading process, the crystallinity of copper phthalocyanine changes due to heat and shear.

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

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

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-type kneader such as a pressure kneader or a Bambary mixer or a continuous-type kneader can be used. Due to the superiority of continuous production, single-screw or two-screw extruders have become the mainstream. for example,
KTK type 2-axis extruder (manufactured by Kobe Steel, Ltd.),
TEM type 2-axis extruder (manufactured by Toshiba Machine Co., Ltd.),
PCM kneader (manufactured by Ikekai Co., Ltd.),
2-axis extruder (manufactured by K.C.K.),
Ko Kneader (manufactured by Bus),
Kneedex (manufactured by Nippon Coke Industries Co., Ltd.)
And so on.

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

The kneading machine used in the examples described later is a biaxial extruder in the same direction.

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

The raw material mixture is supplied from one end of the kneading shaft, is heated and kneaded by the rotation of the kneading shaft while being in a molten state, and is extruded from the other end. Vent holes may be installed along the way for the main purpose of degassing.

The cross section of the kneading shaft may be propeller-shaped or triangular. It is set out of phase so that one tip always rotates to rub the other. This structure has a self-cleaning action of sending the kneaded material forward while suppressing the adhering of the kneaded material to the kneading shaft and the barrel wall.

The rotation directions of the two kneading shafts are preferably the same. By rotating the kneading shaft in the same direction, an appropriate shearing force can be applied. When an appropriate shearing force is applied, the copper phthalocyanine is uniformly dispersed, and the crystal growth of the 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 may grow into crystals and the coloring power may decrease.

The kneading shaft is roughly divided into two types, one is a feed screw part and the other is a kneading part. The screw part has a function of feeding the kneaded material forward while heating it. When the viscosity of the kneaded material in the cylinder is high, it is kneaded by the shearing force due to the friction between the wall of the screw portion and the kneaded material, but when the viscosity is low, it is hardly kneaded. The kneading part has almost no effect of sending the kneaded material forward, and the kneaded material stays and fills.

When producing the toner of the present invention, the difference (Tb-Ta) between the barrel set temperature (Ta) of the kneading portion and the temperature (Tb) of the kneaded product is preferably 30 ° C. or higher and 90 ° C. or lower, preferably 40 ° C. It is more preferable to keep the temperature below 70 ° C. 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 rotation speed of the kneading shaft, and the feed amount. When Tb-Ta (° C.) is less than 30 ° C., the effect of compression and stretching due to the rotation of the kneading shaft performed in the kneading portion is small. Therefore, the share of copper phthalocyanine crystals is weakened. When Tb-Ta (° C.) exceeds 90 ° C., the share of the copper phthalocyanine crystals is too strong, and the crystals tend to collapse. If the crystals collapse, the color development of the toner may decrease.

The cooled product of the kneaded product is pulverized to a desired particle size in the pulverization step. In the pulverization step, after coarse pulverization with a pulverizer, further pulverization is performed with a fine pulverizer. Examples of the crusher for coarse crushing include a crusher, a hammer mill, and a feather mill. Examples of the pulverizing machine for pulverizing include a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industries, Ltd.), and an air jet. Examples include a fine crusher according to the method.

Then, if necessary, the toner particles are classified using a classifier or a sieving machine to obtain toner particles. As a classifier or a sieving machine, for example,
Inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.),
Centrifugal force classification turboplex (manufactured by Hosokawa Micron Co., Ltd.),
TSP Separator (manufactured by Hosokawa Micron Co., Ltd.),
Faculti (manufactured by Hosokawa Micron Co., Ltd.)
And so on.

After that, if necessary, for example, an external agent such as inorganic fine particles or resin particles is added and mixed (external) with the toner particles in order to impart fluidity to the toner or to make the toner chargeable appropriately. Thereby, toner is obtained. The mixing device can be performed by a mixing device having a rotating body having a stirring member and a main body casing provided with a gap between the stirring member.

As a mixing device, for example
Henschel Mixer (manufactured by 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 Co., Ltd.), Spiral Pin Mixer (manufactured by Pacific Kiko Co., Ltd.),
Ladyge Mixer (manufactured by Matsubo Co., Ltd.)
And so on. In particular, a Henschel mixer (manufactured by Mitsui Mine Co., Ltd.) is suitable for uniformly mixing the external additive and the toner particles to loosen the aggregates of the external additive.

Examples of the mixing conditions include the amount of processing, the number of rotations of the stirring shaft, the stirring time, the shape of the stirring blade, the temperature inside the tank, and the like.

If the coarse agglomerates of the additive are free and present in the obtained toner, a sieving machine or the like may be used, if necessary.

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

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

First, the sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter (trade name: Maeshori 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. This sample solution is used for measurement under the following conditions.

Equipment: HLC8120GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series 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 the molecular weight calibration curve created using.

[Measuring method of softening point of resin]
The softening point of the resin is measured using a constant load extrusion type thin tube 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 a piston, the temperature of the measurement sample filled in the cylinder is raised 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 and temperature can be obtained.

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

The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) /. 2). The temperature of the flow curve when the amount of descent of the piston becomes 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 in an environment of 25 ° C. using a tablet molding compressor (trade name: NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. A columnar product having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rise method Start temperature: 40 ° C
Reaching temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise 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: 1.0 mm

[Method for measuring acid value of resin]
The acid value is the mass [mg] of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K0070-1992. Specifically, the measurement is performed according to the following procedure.

(1) Preparation of Reagents 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.

Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. As for the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in a triangular flask, add a few drops of the phenolphthaline solution, titrate with the potassium hydroxide solution, and neutralize the potassium hydroxide. Obtained from the amount of solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K8001-1998 are used.

(2) Operation (A) 2.0 g of this test sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution as an indicator are added, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues 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) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: sample (g).

[Measuring 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, the measurement is performed according to the following procedure.

(1) Preparation of reagent Put 25 g of special grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake well to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, or the like.

Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to 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 make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. As for the factor of the potassium hydroxide solution, take 25 mL of 0.5 mol / L hydrochloric acid in a triangular flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and neutralize the potassium hydroxide. Obtained from the amount of solution. As the 0.5 mol / L hydrochloric acid, the one prepared according to JIS K8001-1998 is used.

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

A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed about 1 cm in a glycerin bath at about 97 ° C. and heated. 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 thick paper having a round hole.

After 1 hour, remove the flask from the glycerin bath and allow to cool. After allowing to cool, add 1 mL of water from the funnel and shake to hydrolyze acetic anhydride. In addition, the flask is heated again in a glycerin bath for 10 minutes for complete hydrolysis. After allowing to cool, wash the walls of the funnel and flask with 5 mL of ethyl alcohol.

Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.

(B) Blank test Perform the same titration as the above operation except that the binder resin sample is not used.

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

[Measurement of maximum endothermic peaks of wax and crystalline polyester resin]
The peak temperature of the maximum endothermic peak of wax is measured according to ASTM D3418-82 using a differential scanning calorimeter (trade name: Q1000, manufactured by TA Instruments). The melting point of indium and zinc is used for the temperature correction of the device detection unit, and the heat of fusion of indium is used for the correction of the calorific value.

Specifically, about 5 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is in the measurement temperature range of 30 ° C to 200 ° C. Measure at 10 ° C./min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then raised again. The temperature showing the maximum endothermic peak of the DSC curve in the range of 30 ° C. or higher and 200 ° C. or lower 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]
For X-ray diffraction measurement, a measuring device (trade name: RINT-TTRII, manufactured by Rigaku Co., Ltd.) and control software and analysis software attached to the device are used.

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 vertical limiting slit: 10.00 mm
Scattering slit: Open Light receiving slit: Open Counter: Scintillation counter Scanning mode: Continuous Scanning speed: 4.0000 ° / min.
Sampling width: 0.0200 °
Scanning axis: 2θ / θ
Scanning range: 10.000 ° to 40.0000 °

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

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

[Production example of binder resin 1]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 76.9 parts by mass (0.167 mol),
24.1 parts by mass (0.145 mol) of terephthalic acid,
8.0 parts by mass (0.054 mol) of adipic acid, and
0.5 parts by mass of titanium tetrabutoxide was placed in a 4 L glass 4-necked flask, fitted with a thermometer, stirring rod, condenser and nitrogen inlet tube, 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 4 hours while stirring at a temperature of 200 ° C. (first reaction step).

Then, 1.2 parts by mass (0.006 mol) of anhydrous trimellitic acid was added and reacted at 180 ° C. for 1 hour (second reaction step) to obtain a binder resin 1.

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

[Production example of binder resin 2]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 71.3 parts by mass (0.155 mol),
24.1 parts by mass (0.145 mol) of terephthalic acid, and
0.6 parts by mass of titanium tetrabutoxide was placed in a glass 4 L four-necked flask, fitted with a thermometer, stirring rod, condenser and nitrogen inlet tube, 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).

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

The acid value of the binder resin 2 was 15 mgKOH / g, and the hydroxyl value was 7 mgKOH / g. The molecular weight by GPC was 200,000 for the weight average molecular weight (Mw), 5,000 for the number average molecular weight (Mn), and 10,000 for the peak molecular weight (Mp). 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% based on the total number of moles of polyhydric alcohol), and
66.1 parts by mass of dodecanedioic acid (0.29 mol, 100.0 mol% based on the total number of moles of polyvalent carboxylic acid)
Weighed and placed in a reaction vessel with a condenser, stirrer, nitrogen introduction tube and thermocouple.

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 3 hours while stirring at a temperature of 140 ° C.

Then, 0.5 part by mass of tin 2-ethylhexanoate was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C.

Then, 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 Examples 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 those in 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 placed to dissolve the hydrocarbon wax. Then, 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 added dropwise at 180 ° C. for 3 hours to polymerize them. Further, it was held at this temperature for 30 minutes. Next, the solvent was removed to obtain the polymer 1.

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

[Manufacturing example of toner 1]
Bundling resin 1 70.0 parts by mass,
Bundling resin 2 30.0 parts by mass,
Crystalline polyester resin 1 7.5 parts by mass,
Fischer-Tropsch wax (peak temperature of maximum endothermic peak: 90 ° C) 5.0 parts by mass,
Polymer 1 5.0 parts by mass and
C. I. Pigment Blue 15: 3 5.0 parts by mass was mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20 seconds- ¹ and a rotation time of 5 minutes. After that, the melt kneading condition 1 in Table 3 (set temperature of the kneading shaft C0: 30 ° C., C1: 70 ° C., C2: 90 ° C., C3 = barrel set temperature of the kneading portion Ta: 90 ° C., C4: 90 ° C., The kneading was carried out with a two-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 product 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 product was 150 ° C.

The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to 1 mm or less to obtain a coarsely crushed product.

The obtained coarse crushed product was finely pulverized with a mechanical crusher (trade name: T-250, manufactured by Turbo Industries, Ltd.).

Further, classification was performed using a rotary classifier (trade name: 200TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) were set to a classification rotor rotation speed of 50.0 seconds- ¹ .

The obtained toner particles had a weight average particle size (D4) of 6.2 μm.
To 100 parts by mass of the obtained toner particles, 0.8 parts by mass of hydrophobic silica fine particles having a number average particle size 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 Mine 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.

[Manufacturing example 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 amounts used for each were changed. Manufactured.

[Production example of magnetic core particles 1]
-Step 1 (Weighing / mixing step):
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 part by mass was weighed. Then, these were placed in a dry vibration mill using stainless steel beads having a diameter of 1/8 inch, crushed for 5 hours, and mixed.

-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by 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 opening of 0.5 mm. Then, using a burner type firing furnace, the calcined ferrite was prepared by firing in a nitrogen atmosphere (oxygen concentration 0.01% by volume) at a temperature of 1000 ° C. for 4 hours.

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 (crushing step):
It was crushed to about 0.3 mm with a crusher. Then, 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 with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

・ Process 4 (granulation process):
To 100 parts by mass of calcined ferrite, 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 the ferrite slurry. Then, it was granulated into spherical particles with a spray dryer (manufactured by Okawara Kakoki Co., Ltd.). After adjusting the particle size of the obtained particles, the particles were heated at 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.

-Step 5 (firing step):
In order to control the firing atmosphere, the temperature was raised from room temperature to a temperature of 1300 ° C. in 2 hours under a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace. Then, it was calcined at a temperature of 1150 ° C. for 4 hours. Then, over 4 hours, the temperature was lowered to 60 ° C., the nitrogen atmosphere was returned to the atmosphere, and the mixture was taken out at a temperature of 40 ° C. or lower.

・ Process 6 (sorting process):
The agglomerated particles were crushed. Then, the low magnetic force product was cut by magnetic beneficiation and sieved with a sieve having a mesh size of 250 μm to remove coarse particles to obtain magnetic core particles 1 having a 50% particle size (D50) of 37.0 μm based on the volume distribution. ..

[Preparation of coating resin 1]
Cyclohexyl methacrylate monomer 26.8 parts by mass,
Methyl methacrylate monomer 0.2 parts by mass,
Methyl methacrylate macromonomer (macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000) 8.4 parts by mass,
Toluene 31.3 parts by mass,
Methyl ethyl ketone 31.3 parts by mass and
Of the 2.0 parts by mass of azobisisobutyronitrile, four flasks equipped with cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone, a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. It was added to a separable flask. Then, after introducing nitrogen gas to create a nitrogen atmosphere, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours to polymerize them.

Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration. Then, it was vacuum dried to obtain a coated resin 1. 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) : Regal330, manufactured by Cabot Corporation) 0.3 parts by mass was dispersed with a paint shaker using zirconia beads having a diameter of 0.5 mm for 1 hour. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coated resin solution 1.

[Manufacturing example of magnetic carrier 1]
(Resin coating process):
The coated resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the packed core particles 1. After charging, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes to volatilize the solvent above a certain level (80% by mass). Then, the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled.

The obtained magnetic carrier is separated into low magnetic force products by magnetic beneficiation, passed through a sieve having an opening of 70 μm, and then classified by a wind power classifier. I got 1.

[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 The magnetic carrier 1 was mixed to obtain a two-component developer 1.

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

The following evaluations were carried out using the two-component developing agents 1 to 18 as the two-component developing agents of Examples 1 to 15 and Comparative Examples 1 to 3.

The evaluation results of Examples 1 to 15 and Comparative Examples 1 to 3 are shown in Table 6.

(Evaluation method of toner coloring power)
As an image forming apparatus, a modified machine of a full-color copying machine (trade name: imageRUNNER ADVANCE C5255) manufactured by Canon Inc. was used, and the two-component developer 1 was put into the developer of the cyan station for evaluation.

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

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

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

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

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

From the toner loading 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

(Evaluation method of fog on non-image part)
As the image forming apparatus, the same modified machine as above was used, and the two-component developer 1 was put into the developer of the cyan station and evaluated.

The evaluation environment was a normal temperature and 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.

In each environment, fog on the white background after the durability test was measured.

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

After the durability test (50,000th sheet), the reflectance Ds (%) of the 00H image portion (white background portion) was measured. From the obtained Dr and Ds, the fog value (%) was calculated 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% (fog cannot be confirmed visually)
B: 0.5% or more and less than 1.0% (fog value is larger than A, but fog cannot be visually confirmed.)
C: 1.0% or more and less than 2.0% (fog can only be slightly confirmed visually.)
D: 2.0% or more (fog can be visually confirmed)

Claims (6)

A toner having toner particles containing crystals of a binder resin and copper phthalocyanine.
The crystals of the copper phthalocyanine have a half-value width of 0.30 ° or more and 0. A toner characterized by having a diffraction peak of 34 ° or less. The toner according to claim 1, wherein the content of the copper phthalocyanine crystals in the toner particles is 0.1 part 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 or 2, wherein the binder resin contains a crystalline polyester resin. The crystalline polyester resin
Aliphatic diols with 6 or more and 12 or less carbon atoms, and
The toner according to claim 3 , which is a polycondensation polymer of an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms. It said toner particles further contain a polymer scan Chiren'akuriru polymer is graft-polymerized to a polyolefin,
The styrene-acrylic polymer, the toner according to any one of claims 1 to 4 have a unit represented by the following formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a saturated alicyclic group.) A method for producing a toner according to any one of claims 1 to 5.
The manufacturing method comprises a melt-kneading step of melt-kneading a mixture containing the binder resin and the copper phthalocyanine by a twin-screw extruder having a kneading shaft.
When the barrel set temperature of the kneading portion of the kneading shaft in the melt-kneading step is Ta (° C.) and the temperature of the kneaded product obtained by the melt-kneading step is Tb (° C.), Ta and Tb are 30. A method for producing a toner, which comprises satisfying ≦ Tb−Ta ≦ 90.

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