JP5995669B2 - toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography or electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method.

  Studies for improving the triboelectric charging characteristics of toners have been actively conducted. In particular, in recent years, proposals have been made to use a resin having a charge control function (charge control resin) as a toner raw material because of environmental considerations, more stable chargeability requirements, manufacturing costs, and the like. . For example, a toner using a resin containing a neutralized salt of vinyl benzoic acid as a monomer unit as a charge control resin has been proposed (Patent Document 1). According to this method, it is said that a toner having a quick rise in charge, a sharp charge distribution, and excellent environmental stability and stability over time can be obtained. In addition, a toner produced by a suspension polymerization method using a composition liquid containing a vinyl benzoic acid monomer or a polymer having vinyl benzoic acid has been proposed. (Patent Document 2) According to this method, it is said that a toner having a fast charge rising and good chargeability can be obtained. In addition, a toner using a resin containing a sulfonic acid group as a charge control resin has been proposed (Patent Document 3). According to this method, it is said that a change in charge amount due to environmental change is small and a toner having stable charging characteristics can be obtained.

JP-A 63-88565 Japanese Patent Laid-Open No. 11-72955 Japanese Patent No. 2807955

However, even when such measures are used, there is still room for improvement in the rising characteristics and durability stability of charging in a high temperature and high humidity environment.
An object of the present invention is to provide a toner having good charge rising even in a high temperature and high humidity environment and having excellent durability stability.

  The present invention relates to a toner having toner particles containing a binder resin and a colorant, and a polar resin or a charge control agent, wherein the toner particles have an aromatic group having a carboxyl group represented by the following formula (1). The present invention relates to a toner containing a compound.

（式中、Ｒ^９は、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシル基を表し、Ｒ^１０は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシル基を表し、Ｒ^１１は、水素原子、又は、メチル基を表し、ｍは、０以上３以下の整数を表し、ｍが２又は３の場合、Ｒ^９はそれぞれ独立して選択でき、ｎは、１以上３以下の整数を表す。）

(In the formula, R ⁹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 18 carbon atoms. A group or an alkoxyl group having 1 to 18 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 3 and when m is 2 or 3, R ⁹ can be independently selected, and n represents an integer of 1 to 3.

  According to the present invention, it is possible to obtain a toner having good charge rising even in a high temperature and high humidity environment and having excellent durability stability.

FIG. 3 is a diagram illustrating a configuration of an apparatus used for measuring a triboelectric charge amount of a developer using the toner of the present invention.

  By incorporating an aromatic compound having a carboxyl group represented by the following formula (1) into toner particles having frictional charging performance, the present inventors have good charge rising even in a high temperature and high humidity environment. Thus, the inventors have found that it is possible to obtain a toner having excellent durability and stability, and have reached the present invention.

（式中、Ｒ^９は、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシル基を表し、Ｒ^１０は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシル基を表し、Ｒ^１１は、水素原子、又は、メチル基を表し、ｍは、０以上３以下の整数を表し、ｍが２又は３の場合、Ｒ^９はそれぞれ独立して選択でき、ｎは、１以上３以下の整数を表す。）

(In the formula, R ⁹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 18 carbon atoms. A group or an alkoxyl group having 1 to 18 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 3 and when m is 2 or 3, R ⁹ can be independently selected, and n represents an integer of 1 to 3.

Generally, the triboelectric charge generated on the toner surface is easily affected by the absolute water content on the toner surface. This is because water molecules are greatly involved in charge transfer, and when the frequency of desorption of water molecules on the toner surface increases under high humidity, the charge leakage rate increases, and the saturation charge amount decreases and the charge amount rise rate increases. This is thought to be due to a decrease.
However, as in the present invention, the presence of the aromatic compound having a carboxyl group represented by the formula (1) in the toner particles stably maintains the charge generated by frictional charging even in a high temperature and high humidity environment. It becomes difficult to be influenced by external temperature and humidity.

  Although the mechanism is not clear, the present inventors consider as follows. The spread of conjugated systems such as oxygen atoms and aryl groups present in the components having the above-described structure is considered to improve the charge transfer speed and increase the charge start-up performance. . On the other hand, when excessive charging (overcharging) occurs, the effect of preventing the local overcharging by releasing the charge promptly is expected.

  The aromatic compound having a carboxyl group represented by the formula (1) has a structure in which an aromatic ring and a benzoic acid structure are bonded via an alkyl ether advantageous for electron conduction. The large conjugated structure extending from this benzoic acid derivative plays a role of holding the charge generated by frictional charging inside the molecule while minimizing the influence of external temperature and humidity, and gives the toner a stable chargeability. Conceivable.

  Specific examples of the aromatic compound having a carboxyl group represented by the above formula (1) are shown in Table 1. The examples shown here are merely examples, and the present invention is not limited to these examples.

The toner of the present invention preferably contains 0.10 μmol or more and 200 μmol or less of an aromatic compound having a carboxyl group represented by the formula (1) per gram of toner, and preferably contains 2.0 μmol or more and 120 μmol or less. More preferred. When the content is within the above range, the charge retention performance inside the toner becomes better. Note that the content of the toner of the present invention can be controlled by adjusting the amount of the component at the time of toner preparation. The content of the aromatic compound in the toner, which will be described later, is calculated and obtained from the charged amount of the aromatic compound at the time of toner preparation.

  The toner of the present invention contains a charge imparting component such as a binder resin and a colorant, and a polar resin or a charge control agent in addition to the aromatic compound represented by the formula (1). Here, the charge imparting component may be any component that can be tribocharged to such an extent that it can be used as a toner, and is a polar resin or a compound known as a known charge control agent having positive chargeability or negative chargeability. Can be used. The charge imparting component includes a case where the binder resin and the polar resin are contained, a case where the binder resin and the charge control agent are contained, and a case where the binder resin itself is a polar resin.

The compounds known as positively or negatively chargeable charge control agents include, for example, organometallic complexes or chelate compounds, quaternary ammonium salts, nigrosine dyes, azine dyes, triphenylmethane dyes and the like. . Of these, organometallic complexes or chelate compounds having positive chargeability or negative chargeability are preferable. Specific examples include a metal compound of a monoazo dye, a metal compound of acetylacetone, a metal compound of an aromatic dicarboxylic acid, a metal compound of an aromatic hydroxycarboxylic acid, and a metal compound of benzyl acid.
In the toner of the present invention, when the binder resin and the charge control agent are contained, the content of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. It is preferably 0.50 parts by mass or more and 10 parts by mass or less.

The polar resin is a resin that easily causes triboelectric charging, that is, a resin that is relatively easy to exchange charges, and includes known polar resins used for toner. Examples of the resin include those having an ether bond, an ester bond, an amide bond, and the like, and those having a polar group such as a carboxyl group, a sulfonic acid group, and a hydroxyl group. Specific examples include polyester resins, polyether resins, polyamide resins, styrene-acrylic resins having a carboxyl group, a sulfonic acid group, and a hydroxyl group, and a hybrid resin in which they are bonded. it can. Further, the vinyl polymer unit in the vinyl resin or the hybrid resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
Among them, polar resins having an acid value are easily charged and the amount of charge tends to be high, which is effective as a toner material. Examples of the resin having an acid value include a polyester resin and a styrene acrylic resin containing a unit having a carboxyl group or a sulfonic acid group.
Examples of the polyester resin having an acid value include a resin having a carboxyl group at the terminal. Further, it may be a polyester synthesized by using a trifunctional or higher polyvalent carboxylic acid as a monomer, and a resin in which a part of the carboxyl group remains without being esterified.

As monomers having high polarity among the monomers constituting the styrene acrylic resin, known ones can be used, and specific examples include the following. Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, α, β-unsaturated acids and the like An anhydride with a lower fatty acid; a monomer having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof. Acrylic acid esters or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) A monomer having a hydroxyl group such as methylhexyl) styrene; Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half esters of unsaturated dibasic acids such as acid methyl half esters, methyl fumarate half esters and methyl mesaconic acid half esters. Monomers having an unsaturated sulfonic acid such as parastyrene sulfonic acid.

  Specific examples of the monomer that can be copolymerized with the monomer having the polarity include the following. Styrene and derivatives thereof such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; vinyl chloride, vinylidene chloride, Vinyl halides such as vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; acrylic acid esters such as acrylic acid-n-butyl and acrylic acid-2-ethylhexyl; Methacrylic acid esters obtained by changing the acrylic acid of the acrylic acid esters to methacrylic acid; methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Le acids; such vinyl ketones of vinyl methyl ketone; N- vinyl pyrrole, such as N- vinyl compounds, vinyl naphthalenes; acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide. In addition, you may use a vinyl monomer in combination of 2 or more type as needed.

The polymerization initiator that can be used in the production of the styrene acrylic resin is not particularly limited, and a known peroxide polymerization initiator or azo polymerization initiator can be used.
Examples of organic peroxide polymerization initiators include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides.
Examples of inorganic peroxide polymerization initiators include t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypirate. Peroxyesters such as barate, t-hexylperoxyisobutyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; diisopropylperoxydi Peroxydicarbonates such as carbonate; peroxyketals such as 1,1-di-t-hexylperoxycyclohexane; dialkyl peroxides such as di-t-butyl peroxide; t-butylperoxyallyl monocarbonate Boneto and the like. As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate).

On the other hand, a polyester resin having an acid value is produced by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component.
The following are mentioned as a polyhydric alcohol component which comprises this polyester resin. Specifically, as the dihydric alcohol component, 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- Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2 -Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neope Til glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, Hydrogenated bisphenol A is mentioned.
Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. .
Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Examples thereof include succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.
Among them, in particular, a bisphenol derivative is a diol component, and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof is an acid component (eg, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid) , Trimellitic acid, pyromellitic acid, etc.) polyester resins obtained by condensation polymerization of these can be preferably used.

The hybrid resin is preferably a hybrid resin having a polyester structure as a main skeleton and modified with a vinyl monomer.
As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used. Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator, a method of graft-modifying a polyester resin having an unsaturated group, and a hybrid resin.
In the toner of the present invention, when the binder resin and the polar resin are contained, the content of the polar resin is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the binder resin. That's it. As described above, in the present invention, when the binder resin itself is a polar resin, the polar resin is used as the binder resin constituting the toner.

  In the present invention, the acid value of the resin can be given as an index indicating the polarity. In the present invention, the acid value of the polar resin is preferably 2.0 mgKOH / g or more and 60.0 mgKOH / g or less, and more preferably 4.0 mgKOH / g or more and 30.0 mgKOH / g or less. If it is said range, since a moderate electric charge can be hold | maintained and water absorption can be suppressed low, it becomes a more suitable thing.

  A method for adjusting the acid value of the polar resin will be described. In the case of a styrene acrylic resin, it can be adjusted by the amount of acid component charged as a monomer that gives an acid value. In the case of a polyester resin, the amount of acid groups and hydroxyl groups can be adjusted by the ratio of the amount of the polyhydric alcohol component to the polyvalent carboxylic acid component.

  In the present invention, it is preferable to control the surface acid value of the toner particles. The surface acid value of the toner is an acid value measured when the toner is dispersed in an aqueous medium, and the measuring method will be described later. The surface acid value of the toner particles is preferably 0.050 mgKOH / g or more and 1.000 mgKOH / g or less. This is presumably because the chargeability of the toner depends on the acid value of the toner surface. In order to control the surface acid value of the toner, it is preferable to mainly control the acid value of the resin introduced into the toner particles. In the case of a toner prepared by granulation in an aqueous medium, this can be achieved by adjusting the acid value of a relatively hydrophilic resin that easily migrates to the toner surface.

The toner of the present invention can be manufactured by various manufacturing methods.
For example, a kneading and pulverizing method in which toner particles are obtained by mixing binder resin and colorant, polar resin or charge control agent, and other releasing agents as necessary, and kneading, pulverizing, and classifying steps; Dissolve suspension to obtain toner particles by dissolving or dispersing and mixing binder resin and colorant, polar resin or charge control agent, and other release agent if necessary, granulating in aqueous medium Method: Binder resin and colorant, polar resin or charge control agent, and other fine particles of a release agent as required are finely dispersed in an aqueous medium, and agglomerate them into a toner particle size to obtain toner particles. Examples thereof include an emulsion aggregation method. Then, when the toner particles are produced by the above method, an aromatic compound having a carboxyl group represented by the formula (1) may be contained.

Examples of the colorant that can be used in the toner of the present invention include known colorants such as various conventionally known dyes and pigments.
Examples of the color pigment for magenta include C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment Violet 19, 23. These pigments may be used alone or in combination with a dye and a pigment.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 15, 15: 1, 15: 3 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185.

As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those that are toned in black using the yellow, magenta, and cyan colorants shown above can be used.
The content of these colorants is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner of the present invention can also be used as a magnetic toner. In this case, the following magnetic materials are used. Iron oxide including magnetite, maghemite, ferrite, or other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Alloys with metals such as Zn, Sb, Ca, Mn, Se, Ti, and mixtures thereof. More specifically, triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ), oxidation Examples thereof include iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), and iron oxide manganese (MnFe ₂ O ₄ ). The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.
These magnetic materials preferably have an average particle size of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.3 μm. The magnetic characteristics when 795.8 kA / m (10 k Oersted) is applied are such that the coercive force (Hc) is 1.6 kA / m to 12 kA / m (20 Oersted to 150 Oersted), and saturation magnetization (σs ) Is preferably ⁵ Am ² / kg or more and 200 Am ² / kg or less, more preferably 50 Am ² / kg or more and 100 Am ² / kg or less. Residual magnetization (.sigma.r) is, ^2Am 2 / kg or more 20 Am ² / kg or less being preferred.
The magnetic body is preferably used in the range of 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain a release agent. The release agent includes aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbon waxes Block copolymers of these: waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; and fatty acid esters such as deoxidized carnauba wax that are partially or fully deoxidized, behenic acid Examples thereof include partially esterified products of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  As for the molecular weight distribution of the release agent, the main peak is preferably in a region having a molecular weight of 400 or more and 2400 or less, and more preferably in a region of 430 or more and 2000 or less. Thereby, preferable thermal characteristics can be imparted to the toner. The amount of the release agent added is preferably 2.5 parts by mass or more and 40.0 parts by mass or less, and 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.

In the toner of the present invention, it is preferable that a fluidity improver is externally added to the toner particles. A toner having a fluidity improver on the surface of the toner particles can be obtained by sufficiently mixing the toner particles and the fluidity improver using a mixing machine such as a Henschel mixer. Examples of the fluidity improver include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder obtained by a wet process, silica fine powder such as a silica fine powder obtained by a dry process, and silica fine powders. Treated silica fine powder surface treated with a treatment agent such as silane coupling agent, titanium coupling agent, silicone oil; titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder . The fluidity improver preferably has a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more, as measured by a BET method using nitrogen adsorption. The addition amount of the fluidity improver is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.1 parts by mass or more and 4.0 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

  The weight average particle diameter (D4) of the toner of the present invention is preferably 3.0 μm or more and 15.0 μm or less, more preferably 4.0 μm or more and 12.0 μm or less.

The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. As magnetic carriers, surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, their alloy particles, oxide particles and ferrite are atomized. Can be used.
When image formation is performed using a developing method in which an AC bias is applied to the developing sleeve, it is preferable to use a coated carrier in which the surface of the magnetic carrier core is coated with a resin. Examples of the coating method include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is attached to the surface of the magnetic carrier core, and a method in which the magnetic carrier core and the coating material are mixed in a powder state. Used.
Examples of the coating material for the magnetic carrier core include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in plurality. The treatment amount of the coating material is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less with respect to the magnetic carrier core particles. The magnetic carrier preferably has a volume-based 50% particle size (D50) of 10 μm to 100 μm, and more preferably 20 μm to 70 μm. When preparing a two-component developer, the mixing ratio is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less as the toner concentration in the developer.

  The measurement method used in the present invention will be described below.

<Molecular weight measurement of resin>
The molecular weight and molecular weight distribution of the resin used in the present invention are calculated in terms of polystyrene by gel permeation chromatography (GPC). For the resin having an acid group, the column elution rate also depends on the amount of the acid group, so a sample in which the acid group is capped in advance is prepared. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.
The molecular weight is measured by GPC as follows. The above resin was added to THF (tetrahydrofuran), and the solution which was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter having a pore size of 0.2 μm “Mysholy Disc” (manufactured by Tosoh Corporation) to obtain a sample solution. Measure under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of resin may be 0.8 mass%. If the resin is difficult to dissolve in THF, a basic solvent such as DMF can be used.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (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, a molecular weight calibration curve created using standard polystyrene resins listed below is used. Specifically, trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F manufactured by Tosoh Corporation -4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Method for measuring acid value of polar resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Titration is performed using a 0.100 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potential difference titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN (Kyoto Electronics Industry Co., Ltd.)
Titration analysis software: Tview (manufactured by Kyoto Electronics Industry Co., Ltd.)
The titration parameters and control parameters at the time of titration are as follows.
<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic <Control parameters>
End point determination potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL

main exam;
0.100 g of a measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
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 (3: 1) is used).
The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide ethyl alcohol solution, S: Sample (g))

<Measurement method of hydroxyl value of polar resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well 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.
Titration is performed using a 1.0 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.).
100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 1.00 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the hydroxyl value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN (Kyoto Electronics Industry Co., Ltd.)
Titration analysis software: Tview (manufactured by Kyoto Electronics Industry Co., Ltd.)
The titration parameters and control parameters at the time of titration are as follows.
<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic <Control parameter>
End point determination potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL

main exam;
2.00 g of the pulverized measurement sample is precisely weighed into a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to this 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 in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath 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, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol.
The obtained sample is transferred to a 250 mL tall beaker, and 100 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
Blank test Titration is performed in the same manner as above except that no sample is used.
The obtained results are substituted 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 ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide ethyl alcohol solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

<Method for measuring surface acid value of toner particles>
In a glass 300 mL flat bottom beaker, 120 mL of ion exchange water and 30 mL of methanol are added and mixed. In this, 7.5 mL of 1% aqueous solution of sodium dodecylbenzenesulfonate is added as a dispersant to prepare a dispersant solution.
While stirring the dispersant solution in the beaker with a stirrer, 10.00 g of toner particles are added to the dispersant solution little by little and dispersed. Furthermore, ultrasonic dispersion treatment is performed for 60 seconds with an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios). In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower. If the surface acid value of the toner particles is low and it is difficult to disperse in the dispersion, it is effective to appropriately increase the methanol concentration in the dispersion.
The toner dispersion is subjected to neutralization titration using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.).
The surface acid value of the toner particles is calculated by performing titration in the same manner as described above except that the sample solution used in this test in the polar resin acid value measurement method is changed to the toner particle dispersion.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolytic aqueous solution is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In this embodiment, “part” means “part by mass”.

Below, the synthesis example of the aromatic compound which has a carboxyl group represented by Formula (1) is shown. <Synthesis Example of Aromatic Compound A>
100.0 g of p-hydroxybenzoic acid was dissolved in 710 mL of methanol. To this solution, 147.8 g of potassium carbonate was added and heated to 67 ° C. 4- (Chloromethyl) styrene (113.8 g) was dropped into a solution containing p-hydroxybenzoic acid and reacted at 67 ° C. for 12 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in water at pH = 2 and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. This precipitate was dissolved in methanol, dropped into water, reprecipitated, and collected by filtration to obtain a precipitate. This reprecipitation operation was performed twice, and the obtained precipitate was dried at 80 ° C. for 48 hours to obtain 63.5 g of aromatic compound A.

<Synthesis Example of Aromatic Compound B>
281.9 g of 3-hydroxybenzoic acid was dissolved in 2 L of methanol, 414.4 g of potassium carbonate was added, and the mixture was heated to 60 ° C. To this solution, 353.4 g of 4- (chloromethyl) styrene was added and reacted under reflux for 3 hours. The obtained reaction solution was cooled, and methanol was distilled off under reduced pressure to obtain a residue. The obtained residue was dispersed in water with pH = 3, and extracted with ethyl acetate. Thereafter, the organic layer was washed with saturated brine, and then ethyl acetate was distilled off under reduced pressure, followed by recrystallization in ethyl acetate. The obtained precipitate was dried at 60 ° C. for 24 hours to obtain 261.1 g of aromatic compound B having the following structure.

<Synthesis Example of Aromatic Compound C>
168.2 g of 3-hydroxy-3-methoxybenzoic acid was dissolved in 1000 mL of methanol. To this solution, 207.3 g of potassium carbonate was added and heated to 60 ° C. 176.7 g of 4- (chloromethyl) styrene was added dropwise to the solution containing 3-hydroxy-3-methoxybenzoic acid and reacted for 4 hours under reflux. The obtained reaction solution was cooled, and methanol was distilled off under reduced pressure to obtain a residue. The obtained residue was dispersed in water with pH = 3, and extracted with ethyl acetate. Thereafter, the organic layer was washed with saturated brine, and then ethyl acetate was distilled off under reduced pressure, followed by recrystallization in ethyl acetate. The obtained precipitate was dried at 60 ° C. for 24 hours to obtain 115.0 g of an aromatic compound C having the following structure.

<Synthesis Example of Aromatic Compound D>
Aromatic compound D having the following structure is obtained in the same manner as aromatic compound C, except that 3-hydroxy-3-methoxybenzoic acid is changed to 152.1 g of 3-hydroxy-3-methylbenzoic acid. It was.

<Synthesis Example of Aromatic Compound E>
Other than changing 4- (chloromethyl) styrene to a mixture of 3- (chloromethyl) methylstyrene and 4- (chloromethyl) styrene (trade name “CMS-P” manufactured by AGC Seikagaku Co., Ltd.), aromatic Aromatic compound E having the following structure was obtained by the same method as the synthesis of system compound A.

  Next, synthesis examples of resins used in the examples are shown. It shows in Table 2 about the structure and physical property of the obtained resin.

<Synthesis Example of Polyester Resin PES-1>
Bisphenol A / propylene oxide 2.2 mol adduct 67.8 parts terephthalic acid 22.2 parts trimellitic anhydride 10.0 parts dibutyltin oxide 0.005 part is put into a four-necked flask, a thermometer, a stirring rod, A condenser and a nitrogen introduction tube were attached and reacted at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain a polyester resin PES-1.

<Synthesis example of polyester resin PES-2>
Bisphenol A / propylene oxide 2.2 mol adduct 67.0 parts Terephthalic acid 18.0 parts Trimellitic anhydride 15.0 parts Dibutyltin oxide 0.005 part is put into a four-necked flask, and a thermometer, a stirring rod, A condenser and a nitrogen introduction tube were attached and reacted at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain a polyester resin PES-2.

<Synthesis example of polyester resin PES-3>
Bisphenol A / propylene oxide 2.2 mol adduct 65.0 parts terephthalic acid 3.0 parts dimethyl terephthalate 32.0 parts Dibutyltin oxide 0.005 part was placed in a 4 L 4-neck flask made of glass, a thermometer, A stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin PES-3.

<Synthesis example of polyester resin PES-4>
Bisphenol A / propylene oxide 2.2 mol adduct 64.5 parts terephthalic acid 1.5 parts dimethyl terephthalate 34.0 parts Dibutyltin oxide 0.005 part was placed in a 4 L 4-necked flask made of glass, a thermometer, A stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin PES-4.

<Synthesis example of polyester resin PES-5>
Bisphenol A / propylene oxide 2.2 mol adduct 66.0 parts terephthalic acid 21.0 parts trimellitic anhydride 13.0 parts dibutyltin oxide 0.005 part is put into a four-necked flask, a thermometer, a stir bar, A condenser and a nitrogen introduction tube were attached and reacted at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain a polyester resin PES-5.

<Synthesis example of polyester resin PES-6>
Bisphenol A / propylene oxide 2.2 mol adduct 65.0 parts Terephthalic acid 19.0 parts Trimellitic anhydride 16.0 parts Dibutyltin oxide 0.005 part is put into a four-necked flask, and a thermometer, a stirring rod, A condenser and a nitrogen introduction tube were attached and reacted at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain a polyester resin PES-6.

<Synthesis Example of Styrene Acrylic Resin SA-1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.
next,
Styrene 78.0 parts n-butyl acrylate 20.0 parts Methacrylic acid 2.0 parts Dimethyl-2,2′-azobis (2-methylpropionate) 5.0 parts are mixed and stirred in the reaction vessel. Dropped and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain styrene acrylic resin SA-1.

<Synthesis Example of Hybrid Resin HB-1>
Bisphenol A / propylene oxide 2.2 mol adduct 69.0 parts terephthalic acid 28.0 parts fumaric acid 3.0 parts dibutyltin oxide 0.005 part is put into a four-necked flask, a thermometer, a stir bar, a condenser, A nitrogen introduction tube was attached and reacted at 220 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin.
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream. Thereto, 70 parts of the previously prepared polyester resin was added and dissolved.
next,
Styrene 79.0 parts n-Butyl acrylate 20.3 parts Acrylic acid 0.7 parts Dimethyl-2,2'-azobis (2-methylpropionate) 1.5 parts are mixed and stirred in the reaction vessel. Dropped and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain a hybrid resin HB-1.

Toners 1 to 39 were produced by the method described below.
<Example 1>
Polyester resin PES-1 100.0 parts Aromatic compound A 2.8 parts Copper phthalocyanine 5.0 parts (CI Pigment Blue 15: 3: manufactured by Dainichi Seika Co., Ltd.)
-Paraffin wax (HNP-7: manufactured by Nippon Seisaku Co., Ltd.) 3.0 parts The toner material was sufficiently premixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) and then a twin-screw extruder. After melt-kneading and cooling, it was coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the finely pulverized product was classified with a multi-division classifier to obtain toner particles.
Toner 1 was obtained by externally adding 1.0 part of hydrophobic silica fine powder having a BET of 200 m ² / g to 100 parts of the toner particles using a Henschel mixer. Table 3 shows the physical properties of Toner 1. The toner 1 was evaluated as follows. The evaluation results are shown in Table 4.

<Evaluation of rising property of toner charge amount>
Magnetic carrier F813-300 (manufactured by Powder Tech): 282 g and toner 1: 18.0 are put into a plastic bottle with a lid, and 4 times per second with a shaker (YS-LD: Yayoi Co., Ltd.). The mixture was shaken for 1 minute at a reciprocating speed to obtain a two-component developer.
The obtained two-component developer was evaluated as follows.
270 g of the two-component developer was collected and left for 3 days in a high temperature and high humidity environment (30 ° C./80% RH). In the same environment, this was charged into a developing device of a color laser copying machine imageRUNNER ADVANCE C7065 (manufactured by Canon Inc.), and idly rotated with a rotating machine equipped with an external motor. The two-component developer on the developing sleeve was sampled when rotated for 1 minute (Q1 min) and further rotated for 4 minutes (that is, rotated for a total of 5 minutes) (Q5 min). The amount of charge was measured with In the evaluation, (Q5min / Q1min) was calculated and judged according to the following criteria.
A rank: Q5min / Q1min is less than 1.20.
B rank: Q5min / Q1min is 1.20 or more and less than 1.40.
C rank: Q5min / Q1min is 1.40 or more and less than 1.60.
D rank: Q5min / Q1min is 1.60 or more.

(Measurement method of charge amount)
In a metal measuring container 2 having a screen 3 of 500 mesh (aperture 25 μm) at the bottom shown in FIG. 1, 0.500 g of a two-component developer for measuring the triboelectric charge amount is put and a metal lid 4 is placed. The total mass of the measurement container 2 at this time is weighed and is defined as Wl (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner by suction.
The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows.
Frictional charge (mC / kg) = (C × V) / (W1-W2)

<Image output test>
Image evaluation was performed in a high temperature and high humidity (30 ° C./80%) environment using a Canon printer LBP7200C. A cartridge filled with 70 g of toner 1 was installed in the cyan station of the printer, and a dummy cartridge was installed in the others, and an image output test was performed. As image output paper, A4 size white paper GF-C081 (manufactured by Canon Marketing Japan Inc.) was used. Images with a printing rate of 1% were output continuously, and left for 1 week each time the number of output sheets reached 800. Thereafter, the same steps were repeated, and finally 4000 images were output and evaluated by the following method.

(1) Fog evaluation LETTER-size HP Brochure Paper, Glossy (HP, 200 g / m ² ) was used as an evaluation paper. In the above-described image output test, all white images were output one by one (a total of five images) each time after being left for one week. Thereafter, the fog density (%) (=) from the difference between the whiteness (reflectance Ds (%)) of the central portion of the output all white image and the whiteness (reflectance Dr (%)) of the unoutput evaluation paper. Dr (%) − Ds (%)) was calculated. In addition, the whiteness was measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). An amberlite filter was used as the filter. All five images were measured, and the worst value was taken as the measured value. The measurement was ranked as follows. A: The fog density is less than 0.5%.
B: The fog density is 0.5% or more and less than 1.0%.
C: The fog density is 1.0% or more and less than 2.0%.
D: The fog density is 2.0% or more.

(2) Image Density Stability As an evaluation paper, A4 size high white paper GF-C081 (manufactured by Canon Marketing Japan Inc.) was used. The image density was measured with a color reflection densitometer (X-RITE 404 Amanufactured by X-Rite Co.). In the above image output test, before and after being left for one week, a single solid image was output each time (a total of 10 images), and the density at the center of each image was measured. Of the obtained image densities, the difference between the maximum density and the minimum density was determined and shown based on the following evaluation criteria.
A: The image density difference is 0.05 or less.
B: The image density difference is larger than 0.05 and not larger than 0.10.
C: The image density difference is larger than 0.10 and 0.30 or less.
D: The image density difference is larger than 0.30.

<Examples 2 to 16>
With respect to the aromatic compound and the polar resin, toners 2 to 16 were obtained in the same manner as in Example 1 except that the formulation shown in Table 3 was changed. Table 3 shows the physical properties of Toners 2 to 16. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 17>
Preparation of toner composition mixture:
Styrene-n-butyl acrylate copolymer 100.0 parts (mass ratio of styrene and n-butyl acrylate 82:18, Tg 58 ° C., Mw 22000)
Aromatic compound A 3.2 parts copper phthalocyanine 5.0 parts (CI Pigment Blue 15: 3: manufactured by Dainichi Seika Co., Ltd.)
Paraffin wax (HNP-7: manufactured by Nippon Seiki) 8.0 parts Polyester resin PES-1 7.5 parts Ethyl acetate 100.0 parts After pre-mixing the above materials well in a container, keep it below 20 ° C The mixture was dispersed for 4 hours in a bead mill to prepare a toner composition mixed solution.

Preparation of toner particles:
To 240 parts of ion-exchanged water, 78 parts of a 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added, heated to 60 ° C., and stirred at 14,000 rpm using Creamix (manufactured by M Technique). To this, 12 parts of 1.0 mol / L-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.0 part of carboxymethylcellulose (trade name: Cellogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.
While the dispersion medium to which carboxymethyl cellulose has been added is adjusted to 30 ° C. and stirred, 180 parts of the toner composition mixed solution adjusted to 30 ° C. is added, and after stirring for 1 minute, the toner composition is stopped and stopped. A dispersion suspension was obtained. The obtained toner composition dispersion suspension was stirred at a constant temperature of 40 ° C., and the gas phase on the surface of the suspension was forcibly renewed by an evacuation device and kept for 17 hours to remove the solvent. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and toner particles were obtained by filtration, washing with water, drying and classification. To the obtained toner particles, hydrophobic silica fine powder was externally added in the same manner as in Example 1 to obtain toner 17. Table 3 shows the physical properties of Toner 17. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 18>
Production of resin dispersion:
Styrene 78.0 parts n-butyl acrylate 20.0 parts Methacrylic acid 2.0 parts Dodecanethiol 6.0 parts Carbon tetrabromide 1.0 part Nonionic surfactant Nonipol 400 1.5 parts in flask, anion 2.5 parts of anionic surfactant Neogen SC was dissolved in 140 parts of ion-exchanged water. A solution obtained by mixing and dissolving the above materials was dispersed and emulsified in a flask, and 10 parts of ion-exchanged water in which 1.0 part of ammonium persulfate was dissolved was added while slowly mixing for 10 minutes. While performing nitrogen substitution, the flask was heated with an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thereby, the center diameter is 145 nm, the glass transition point is 58 ° C., the acid value is 11.80 mg KOH / g,
A resin dispersion having Mw11200 was obtained.

Preparation of colorant dispersion:
The following composition was mixed and dissolved, and dispersed by homogenizer (IKA Ultra Tarrax) and ultrasonic irradiation to obtain a colorant (cyan pigment) dispersion having a center particle size of 140 nm.
Copper phthalocyanine 100.0 parts (CI Pigment Blue 15: 3: manufactured by Dainichi Seika Co., Ltd.)
Aromatic compound A 60.0 parts Anionic surfactant Neogen SC 10.0 parts Ion-exchanged water 400.0 parts

Preparation of release agent dispersion:
The following composition was mixed, heated to 97 ° C., and then dispersed with IKA Ultra Turrax T50. Thereafter, the mixture was dispersed with a gorin homogenizer (manufactured by Reiwa Shoji Co., Ltd.) and treated 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain a release agent dispersion having a center diameter of 190 nm.
Paraffin wax (HNP-7: manufactured by Nippon Seiki) 100.0 parts Anionic surfactant Neogen SC 5.0 parts Ion-exchanged water 300.0 parts

Toner particle production:
Resin dispersion (resin particle solid content 25.0 mass%) 400.0 parts Colorant dispersion (aromatic compound A content 10.5 mass%) 28.6 parts Release agent dispersion 30.0 parts Sanisol B50 2.0 parts The above was mixed and dispersed in a round stainless steel flask with Ultra Turrax T50, and then heated to 48 ° C. while stirring the flask in a heating oil bath. After maintaining at 48 ° C. for 30 minutes, the temperature of the heating oil bath was further raised and maintained at 50 ° C. for 1 hour. Then, after adding 3 parts of neogen SC here, the stainless steel flask was sealed, heated to 105 ° C. while continuing stirring using a magnetic seal, and held for 3 hours. After cooling, the mixture was filtered, thoroughly washed with ion exchange water, dried and classified to obtain toner particles. Further, in the same manner as in Example 1, the toner particles were obtained by externally adding hydrophobic silica fine powder to the toner particles. Table 3 shows the physical properties of Toner 18. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 19>
Example 1 except that copper phthalocyanine (CI Pigment Blue 15: 3) is changed to carbon black (trade name: Nipex30, manufactured by Degussa) and the polyester resin PES-1 is changed to styrene acrylic resin SA-1. The same operation was performed to obtain toner 19. Table 3 shows the physical properties of Toner 19. Further, the same evaluation as in Example 1 was performed using the obtained toner. (However, in the image output test, the evaluation cartridge was changed to the cyan station and mounted in the black station. Also, the filter at the time of fog measurement was changed from amber to green.) The evaluation results are shown in Table 4.

<Example 20>
Copper phthalocyanine (C.I. Pigment Blue 15: 3) was added to C.I. I. A toner 20 was obtained in the same manner as in Example 19 except that the pigment violet 19 was used. Table 3 shows the physical properties of Toner 20. Further, the same evaluation as in Example 19 was performed using the obtained toner. (However, in the image output test, an evaluation cartridge was mounted on the magenta station.) Table 4 shows the evaluation results.

<Example 21>
Styrene-n-butyl acrylate copolymer 100.0 parts (mass ratio of styrene and n-butyl acrylate 81.5: 18.5, Tg 57 ° C., Mw 21000)
Aromatic compound A 2.9 parts Copper phthalocyanine 5.0 parts (CI Pigment Blue 15: 3: manufactured by Dainichi Seika Co., Ltd.)
Paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.0 parts Boron benzylate compound LR-147 (manufactured by Nippon Carlit Co., Ltd.) 1.6 parts The above toner material is sufficiently premixed by a Henschel mixer (produced by Mitsui Mining Co., Ltd.) After being melted and kneaded with a twin screw extruder, after cooling, it was coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified with a multi-division classifier to obtain toner particles.
To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder having a BET of 200 m ² / g was externally added using a Henschel mixer to obtain toner 21. Table 3 shows the physical properties of Toner 21. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Examples 22 to 25, 27 to 32>
For the aromatic compound and the charge control agent (charging agent), the same operations as in Example 21 were carried out except that the formulation shown in Table 3 was changed, and toners 22 to 25 and 27 to 32 were obtained. Table 3 shows the physical properties of Toners 22 to 25 and 27 to 32. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 26>
A toner 26 was obtained in the same manner as in Example 21 except that the formulation was changed as follows.
Polyester resin PES-1 100.0 parts aromatic compound A 2.9 parts carbon black (trade name: Nippon 30, manufactured by Degussa) 5.0 parts monoazo iron compound (T77: Hodogaya Chemical Co., Ltd.) 5 parts paraffin wax (HNP-7: manufactured by Nippon Seiki) 3.0 parts Table 3 shows the physical properties of Toner 26. Further, the same evaluation as in Example 19 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 33>
Toner 33 was obtained in the same manner as in Example 17 except that 1.6 parts of boron benzylate compound LR-147 (manufactured by Nippon Carlit) was added to the toner composition mixture. Table 3 shows the physical properties of Toner 33. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 34>
A toner 34 was obtained in the same manner as in Example 21, except that the copper phthalocyanine (CI Pigment Blue 15: 3) was changed to carbon black (trade name: Nippon 30, manufactured by Degussa). Table 3 shows the physical properties of Toner 34. Further, the same evaluation as in Example 19 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Example 35>
Copper phthalocyanine (C.I. Pigment Blue 15: 3) was added to C.I. I. Except for changing to Pigment Violet 19, the same operation as in Example 21 was performed to obtain toner 35. Table 3 shows the physical properties of Toner 35. Further, the same evaluation as in Example 20 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Comparative Example 1>
A toner 36 was obtained in the same manner as in Example 1 except that the aromatic compound A was not added. Table 3 shows the physical properties of Toner 36. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Comparative example 2>
Example 1 except that the polyester resin PES-1 is changed to a styrene-n-butyl acrylate copolymer (mass ratio of styrene and n-butyl acrylate 81.5: 18.5, Tg 57 ° C., Mw 21000). Operation was performed to obtain toner 37. Table 3 shows the physical properties of Toner 37. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Comparative Example 3>
A toner 38 was obtained in the same manner as in Example 21 except that the aromatic compound A was not added. Table 3 shows the physical properties of Toner 38. Further, the same evaluation as in Example 1 was performed using the obtained toner. The evaluation results are shown in Table 4.

<Comparative example 4>
A toner 39 was obtained in the same manner as in Example 26 except that the aromatic compound A was not added. Table 3 shows the physical properties of Toner 39. In addition, the same evaluation as in Example 26 was performed using the obtained toner. The evaluation results are shown in Table 4.

1 suction machine, 2 measuring container, 3 screen, 4 lid, 5 vacuum gauge, 6 air volume control valve, 7 suction port, 8 condenser, 9 electrometer

Claims (4)

A toner having toner particles containing a binder resin and a colorant, and a polar resin or a charge control agent, wherein the toner particles contain an aromatic compound having a carboxyl group represented by the following formula (1) Toner.

(In the formula, R ⁹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 18 carbon atoms. A group or an alkoxyl group having 1 to 18 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 3 and when m is 2 or 3, R ⁹ can be independently selected, and n represents an integer of 1 to 3.   The toner according to claim 1, wherein an acid value of the polar resin is 2.0 mgKOH / g or more and 60.0 mgKOH / g or less.   The toner according to claim 1, wherein the charge control agent contains an organometallic complex or a chelate compound having a positive charge property or a negative charge property.   4. The toner according to claim 1, wherein the toner contains 0.10 μmol or more and 200 μmol or less of an aromatic compound having a carboxyl group represented by the formula (1) per 1 g of the toner. The toner described.

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