JP2021056325A - Toner and two-component developer - Google Patents

Abstract

To provide toner and a two-component developer that are excellent in embossed paper transferability and scratch resistance.SOLUTION: A toner includes toner particles having a binder resin and resin fine particles. The resin fine particles are fine particles of vinyl resin. The vinyl resin has a cycloalkyl (meth)acrylate unit and a nitrogen-containing vinyl monomer unit in one molecule. The nitrogen-containing vinyl monomer unit has at least one functional group selected from the group consisting of an amino group, an amide group, an imido group, a urethane bond, a urea bond, a monovalent functional group formed by removing one hydrogen atom from a nitrogen-containing heterocyclic compound, and a quaternary ammonium base.SELECTED DRAWING: None

Description

The present invention relates to a toner and a two-component developer for developing an electrostatic charge image used in an electrophotographic method, an electrostatic recording method, and the like.

In recent years, electrophotographic full-color copiers have become widespread and have begun to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are required while supporting a wide range of media (paper types).

In order to improve the image quality, it is necessary to stabilize the charging characteristics of the toner. In order to stabilize the charging characteristics of toner, various studies have been conducted on external additives. For example, Patent Document 1 discloses a toner in which environmental stability is improved by externally adding vinyl-based resin fine particles containing an amino group.

However, the resin fine particles are inferior in adhesion to the photoconductor, and image defects may occur. As a technique for improving this point, for example, Patent Document 2 discloses a toner externally supplemented with resin fine particles containing an acrylate monomer unit having an isobolonyl group.

Japanese Unexamined Patent Publication No. 2017-15977 Japanese Unexamined Patent Publication No. 2010-92011

However, with regard to high image quality, it is also required to be compatible with multimedia that can be used not only for plain paper but also for various media such as thick paper and thin paper. As the thick paper, not only thick paper having a flat surface but also paper having relatively low surface smoothness such as embossed paper and rough paper having irregularities on the front surface and both front and back surfaces are used. When the surface of the media has irregularities of several tens of μm or more, a gap may be formed in the recessed portion of the media because the transfer member such as a transfer belt cannot contact the media. At the portion where the voids are formed, a discharge due to a transfer bias may occur during transfer. As a result, the charge amount distribution of the toner before transfer is broadened, a part of the toner image is not transferred, and shading may occur in the uneven portion. The transferability to the embossed paper was insufficient with the toners disclosed in Patent Document 1 and Patent Document 2, and further improvement was required.

Furthermore, the stability of printed matter is also important in the printing market. The printed matter may rub against the paper due to vibration during transportation. At that time, when the coefficient of friction between the paper and the image surface is high and the internal aggregation energy is low, even if the image is sufficiently fixed, a part of the image is set off due to scratching and the high image quality state cannot be maintained. was there. The toners disclosed in Patent Document 1 and Patent Document 2 have insufficient scratch resistance, and further improvement is required.

The present invention solves the above-mentioned problems, and provides a toner and a two-component developer having improved embossing transferability and scratch resistance.

The present invention is a toner having toner particles having a binder resin and resin fine particles.
The resin fine particles are vinyl-based resin fine particles.
The vinyl-based resin has a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit in one molecule.
The nitrogen-containing vinyl-based monomer unit includes an amino group, an amide group, an imide group, a urethane bond, a urea bond, a monovalent functional group formed by removing one hydrogen atom from the nitrogen-containing heterocyclic compound, and a monovalent functional group. It has at least one functional group selected from the group consisting of quaternary ammonium bases.
It relates to a toner characterized by that.

Further, the present invention is a two-component developer containing the above toner and a magnetic carrier.
The magnetic carrier has magnetic carrier core particles and a resin coating layer formed on the magnetic carrier core particles.
The resin coating layer contains N element, Si element, and F element.
In elemental analysis by X-ray photoelectron spectroscopy
(I) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected by the surface analysis of the magnetic carrier are N1, S1, and F1 (atom%), respectively. )age,
(Ii) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected at a depth of 40 nm from the surface of the magnetic carrier are N2, S2, respectively. When F2 (atomic%)
The N1, S1, F1, N2, S2 and F2
0.1 ≤ N1 ≤ 1.5
0.3 ≤ S1 ≤ 5.0
45.0 ≤ F1 ≤ 65.0
S1 <S2
S1 / N1 <S2 / N2
F1> F2
The present invention relates to a two-component developer, which is characterized by satisfying the above relationship.

According to the present invention, it is possible to provide a toner and a two-component developer having excellent embossing transferability and scratch resistance.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.

As a result of studying resin fine particles for the purpose of improving image quality, the present inventors have found vinyl resin fine particles having a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit in one molecule. It has been found that by adding external particles, excellent embossing transferability and scratch resistance that have not been obtained in the past can be obtained.

The reason why the effect of the present invention was obtained is considered as follows.

As described above, the main cause of deterioration of embossed transferability is that discharge due to transfer bias occurs in the voids generated during transfer, and the toner before transfer is partially charged in the opposite polarity, resulting in a broad charge distribution. This means that part of the toner image will not be transferred. Therefore, in order to improve the embossing transferability, it is necessary to suppress the broadening of the toner charge amount distribution due to the discharge.

The resin fine particles in the present invention are characterized by having a structure having a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit in one molecule.

By having the nitrogen-containing vinyl-based monomer unit, the resin fine particles in the present invention can be delocalized to the surrounding toner without localizing the charge of the opposite polarity due to the discharge, and the influence of the discharge. Is expected to be relaxed. However, the embossing transferability was not improved only by containing the nitrogen-containing vinyl-based monomer unit. As a result of diligent studies, the present inventors have found that the use of a nitrogen-containing vinyl-containing monomer unit, a cycloalkyl (meth) acrylate unit, and resin fine particles contained in one molecule is effective in improving embossing transferability. I found it. It is considered that the presence of the cycloalkyl (meth) acrylate unit reduces the adhesive force of the toner before transfer and improves the transferability of the toner image.

That is, in the toner of the present invention, by allowing the resin fine particles to exist on the surface of the toner particles, it has become possible to obtain an unprecedented excellent embossing transferability due to the high transferability and the effect of alleviating the reverse polarity charge due to the discharge. ..

Furthermore, it has been found that the toner of the present invention has excellent scratch resistance. There is a phenomenon that a part of the image moves to the scraped side due to rubbing with paper, and the fact that this phenomenon is unlikely to occur means that the scratch resistance is excellent. When the coefficient of friction between the paper and the image surface is high and the internal aggregation energy is low, the phenomenon of image migration is likely to occur even if the image is sufficiently fixed. In the toner externally attached with resin fine particles having a nitrogen-containing vinyl-based monomer unit, the friction coefficient between the paper and the surface of the fixed image becomes high due to the presence of the nitrogen functional group, so that the scratch resistance tends to decrease. However, in the configuration of the present invention, excellent scratch resistance can be obtained.

The toner in which the resin fine particles are present on the surface of the present invention has a low coefficient of friction between the paper and the surface of the fixed image, and the scratch resistance is improved. The reason for this is considered as follows. First, since the vinyl-based resin constituting the resin fine particles has a structure in which a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-containing monomer unit are contained in one molecule, the cycloalkyl is bulkier than the nitrogen functional group. The (meth) acrylate unit is likely to be oriented on the outermost surface of the resin fine particles. It is also considered that the unit derived from the cycloalkyl (meth) acrylate unit is present on the surface of the fixed image, so that the coefficient of friction is reduced and good scratch resistance can be exhibited.

As a result of the above, by using a toner in which resin fine particles having a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit in one molecule are externally added, excellent scratch resistance unprecedented can be obtained. I arrived.

The resin fine particles are not particularly limited as long as they have a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit. Here, the unit refers to a form formed as a result of the reaction of the monomers. In a vinyl resin, it refers to a unit formed by the reaction of vinyl groups contained in a vinyl monomer.

The vinyl resin constituting the resin fine particles may be a polymer of a cycloalkyl (meth) acrylate monomer and a nitrogen-containing vinyl-based monomer, or may be a polymer of other monomers.

Examples of the monomer capable of forming a cycloalkyl (meth) acrylate unit include cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, and cyclopentyl methacrylate. Examples thereof include monomers such as cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, dihydrocyclopentadiethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, isobolonyl acrylate, and isobolonyl methacrylate. These may be used alone or in combination.

Among these, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, isobolonyl acrylate, and isobolonyl methacrylate are preferable from the viewpoint of steric hindrance of the molecular structure.

The monomer that can form a nitrogen-containing vinyl-based unit is a monovalent group formed by removing one hydrogen atom from an amino group, an amide group, an imide group, a urethane bond, a urea bond, or a nitrogen-containing heterocyclic compound. A known nitrogen-containing vinyl-based monomer can be used as long as it has at least one functional group selected from the group consisting of a functional group and a quaternary ammonium base. By having the above functional groups, it is possible to suppress the localization of the charge having the opposite polarity due to the discharge, to delocalize it to the surrounding toner, and to mitigate the influence of the discharge.

Among these, amino group-containing vinyl-based monomers and amide group-containing vinyl-based monomers are preferable.

Examples of the monomer capable of forming the nitrogen-containing vinyl-based unit include the following monomers.

Amino groups such as aminoethyl acrylate, aminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, N-arylphenylenediamine. Containing vinyl-based monomer.

Acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-butylacrylamide, diacetoneacrylamide, N-methylolacrylamide, N, N'-methylene-bisacrylamide, N, N-dimethylacrylamide, N, N Amide group-containing vinyl-based monomers such as −dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, and N-vinylpyrrolidone.

An imide group-containing vinyl-based monomer such as N- (4-vinylphenyl) maleinimide and N-vinylmaleinimide.

A vinyl-based monomer having a urea bond such as N-vinyl-N and N'-trimethylene urea.

From nitrogen-containing heterocyclic compounds such as 4-vinylpyridine, 2-vinylpyridine, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, 9-vinylcarbazole, 4-methyl-5-vinylthiazole, 1-vinylindole. A vinyl-based monomer having a monovalent functional group formed by removing one hydrogen atom.

A vinyl-based monomer having a quaternary ammonium base such as trimethylvinyl ammonium bromide.

Further, the nitrogen-containing vinyl-based monomer unit having a urethane bond can be formed by using, for example, an oligomer of a urethane acrylate having a urethane group and an acrylic group.

Other monomers include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, and benzyl. Styrene-based monomers such as styrene; alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate (the alkyl has a carbon number of carbon). 1 or more and 18 or less); 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; Diene-based monomers such as butadiene and isobutylene. Styrene and a combination thereof can be mentioned.

The volume average particle diameter of the resin fine particles is preferably 0.05 μm or more and 0.50 μm or less, and more preferably 0.10 μm or more and 0.30 μm or less. As a result, the resin fine particles can appropriately coat the toner particles, so that the above-mentioned action is more effectively exhibited, and the embossing transferability and scratch resistance are improved.

A known production method can be used to obtain the resin fine particles in the present invention.

Specifically, the following methods can be mentioned.

(1) A method in which a resin containing a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit is synthesized and then emulsified in an aqueous medium to obtain fine particles.

(2) A method for obtaining fine particles by an emulsion polymerization method using a cycloalkyl (meth) acrylate monomer and a nitrogen-containing vinyl-containing monomer.

By generating the resin fine particles in the aqueous medium, it becomes easy to control the volume average particle size within a preferable range.

The volume average particle size of the resin fine particles is measured using a Microtrack particle size distribution measuring device HRA (X-100) (manufactured by Nikki So Co., Ltd.) in a range setting of 0.001 μm to 10 μm.

The content of the resin fine particles is preferably 0.1 part by mass or more and 5.0 parts by mass or less, and preferably 0.5 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner particles. More preferred. By setting the content of the resin fine particles within the above range, the effects of the resin fine particles described above can be easily obtained, and the embossing transferability and scratch resistance are improved.

The resin fine particles preferably contain the nitrogen-containing vinyl-based monomer unit in an amount of 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. By setting the content of the nitrogen-containing vinyl-based monomer unit within the above range, the influence of electric discharge during transfer can be effectively mitigated, and the friction coefficient of the image surface can be kept low, resulting in embossed transferability. And the scratch resistance becomes good.

The adhesion rate of the resin fine particles to the toner particles is preferably 50% or more, more preferably 70% or more. When the fixing rate is in the above range, a desired amount of resin fine particles is retained on the image surface, so that the effect can be easily obtained, and the embossing transferability and scratch resistance become better.

<Measurement method of adhesion rate of resin fine particles>
(Washing treatment)
Weigh 20 g of a 10 mass% aqueous solution of "Contaminone N" (a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) into a vial having a capacity of 50 mL, and 1 g of toner. Mix with.

Set in "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., set speed to 50, and shake for 30 seconds. As a result, depending on the fixed state of the resin fine particles, the resin fine particles move from the surface of the toner particles to the aqueous solution side.

After that, in the case of magnetic toner, the resin fine particles transferred to the supernatant liquid are separated while the toner particles are restrained using a neodymium magnet, and the precipitated toner is vacuum dried (40 ° C./24 hours). Allow to dry and use as a sample.

In the case of non-magnetic toner, the toner and the resin fine particles transferred to the supernatant are separated by a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) (at 1000 rpm for 5 minutes).

(Measurement)
The toner that has not been washed with water and the dried sample are each observed by SEM, and the resin fine particles existing on the surface of the toner particles are counted and used as the adhesion rate by the following formula.
Adhesion rate (%) = (number of resin fine particles in dried sample) / (number of resin fine particles in toner not washed with water) x 100
For each of the toner and the dried sample, the values measured and averaged for each of 100 samples are used.

A known binder resin can be used as the toner particles. For example, examples of the binder resin include the following.

Styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural resin modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, Polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpen resin, Kumaron inden resin, petroleum resin. Examples of the resin preferably used include a styrene-based copolymer resin, a polyester resin, and a hybrid resin in which a polyester resin and a styrene-based copolymer resin are mixed or both are partially reacted. More preferably, the binder resin includes a polyester resin.

The toner particles in the present invention preferably contain crystalline polyester. By containing the crystalline polyester, the influence of electric discharge at the time of transfer can be more effectively mitigated, and the embossed transferability becomes good. In order to effectively obtain the above characteristics, the content of the crystalline polyester is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

Examples of the alcohol component used in the raw material monomer of crystalline polyester include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7. −Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 Aliphatic diols such as −tetradecanediol, 1,18-octadecanediol and 1,20-icosandiol can be mentioned, but are not limited thereto.

The content of the aliphatic diol is preferably 80 mol% or more and 100 mol% or less in the alcohol component from the viewpoint of further enhancing the crystallinity of the crystalline polyester.

As the alcohol component for obtaining the crystalline polyester, a polyhydric alcohol component other than the above-mentioned aliphatic diol may be contained. For example, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, an alkylene oxide adduct of bisphenol A containing a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane, and the like. Aromatic diols; examples thereof include trihydric or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

On the other hand, examples of the carboxylic acid component used in the raw material monomer of crystalline polyester include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1, Examples thereof include aliphatic dicarboxylic acids such as 10-decandicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecandicarboxylic acid and 1,18-octadecanedicarboxylic acid, and further these anhydrides and their lower alkyls. Esther can also be mentioned.

The content of the aliphatic dicarboxylic acid compound is preferably 80 mol% or more and 100 mol% or less in the carboxylic acid component.

The carboxylic acid component for obtaining the crystalline polyester may contain a carboxylic acid component other than the aliphatic dicarboxylic acid compound. For example, an aromatic dicarboxylic acid compound, a trivalent or higher aromatic polyvalent carboxylic acid compound, and the like can be mentioned, but the present invention is not particularly limited thereto. Aromatic dicarboxylic acid compounds also include aromatic dicarboxylic acid derivatives. Specific examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, anhydrides of these acids, and alkyls thereof (1 carbon number). 3 or less) Esters are preferably mentioned. Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the trivalent or higher valent carboxylic acid compound include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid, and these. Derivatives such as acid anhydrides and alkyl (1 or more and 3 or less carbon atoms) esters can be mentioned.

The molar ratio (carboxylic acid component / alcohol component) of the alcohol component and the carboxylic acid component, which are the raw material monomers of the crystalline polyester resin, is preferably 0.80 or more and 1.20 or less.

The toner of the present invention can be used as any of a magnetic one-component toner, a non-magnetic one-component toner, and a non-magnetic two-component toner.

When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. Examples of the magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxide containing magnetite, maghemite, and ferrite, and magnetic iron oxide containing other metal oxides; metals such as Fe, Co, and Ni, or metals such as Fe, Co, and Ni. Alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and theirs. Examples include mixtures.

The content of the magnetic iron oxide particles is preferably 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin.

Examples of the colorant when used as a non-magnetic one-component toner and a non-magnetic two-component toner include the following.

As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.

As a colorant suitable for yellow color, a pigment or a dye can be used. As the pigment, C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,17,23,62,65,73,74,81,83,93,94,95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Bat Yellow 1, 3, 20 can be mentioned. As the dye, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 and the like can be mentioned. These are used alone or in combination of two or more.

As a colorant suitable for cyan color, a pigment or a dye can be used. As the pigment, C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid blue 45 can be mentioned. As the dye, C.I. I. Solvent blue 25, 36, 60, 70, 93, 95 and the like can be mentioned. These are used alone or in combination of two or more.

As a colorant suitable for magenta color, a pigment or a dye can be used. As the pigment, C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31, 32,37,38,39,40,41,48,48; 2,48; 3,48; 4,49,50,51,52,53,54,55,57,57; 1,58,60, 63,64,68,81,81; 1,83,87,88,89,90,112,114,122,123,144,146,150,163,166,169,177,184,185,202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment Violet 19; C.I. I. Bat red 1,2,10,13,15,23,29,35 can be mentioned. Examples of magenta dyes include C.I. I. Solvent Red 1,3,8,23,24,25,27,30,49,52,58,63,81,82,83,84,100,109,111,121,122, etc., C.I. I. Disperse Thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, etc., C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40, etc., C.I. I. Examples thereof include basic dyes such as Basic Violet 1,3,7,10,14,15,21,25,26,27,28. These are used alone or in combination of two or more.

The content of the colorant 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.

A mold release agent (wax) may be used to impart mold releasability to the toner. Examples of the wax used in the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystallin wax, paraffin wax, Fishertroph wax; oxidized wax of aliphatic hydrocarbon wax such as polyethylene oxide wax; carnauba wax , Waxes mainly composed of fatty acid esters such as behenyl behenate and montanic acid ester wax; and waxes obtained by deoxidizing a part or all of a fatty acid ester such as deoxidized carnauba wax. In addition, saturated linear fatty acids such as palmitic acid, stearic acid and montanoic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol and ceryl alcohol. , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislaurin Saturated fatty acid bisamides such as acid amides and hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'-diorail adipic acid amides, N, N'-diorail sebasic acid amides. Unsaturated fatty acid amides such as; aromatic bisamides such as m-xylenebis stearate amide, N, N'-distearyl isophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate. Group metal salts (generally called metal soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl copolymer monomers such as styrene and acrylic acid; fatty acids such as behenyl acid monoglyceride and many Examples thereof include a partially esterified product of a valent alcohol; a methyl ester compound having a hydroxy group obtained by hydrogenation of a vegetable fat or oil.

A particularly preferably used wax is an aliphatic hydrocarbon wax. For example, low molecular weight hydrocarbons obtained by radical polymerization of alkylene under high pressure or polymerized with Cheegler catalyst or metallocene catalyst under low pressure; Fischer-Tropsch wax synthesized from coal or natural gas; obtained by thermal decomposition of high molecular weight olefin polymer. Olefin polymer; synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbon obtained by the age method from synthetic gas containing carbon monoxide and hydrogen, or synthetic hydrocarbon wax obtained by hydrogenating these is preferable. Further, those obtained by separating the hydrocarbon wax by the press sweating method, the solvent method, the use of vacuum distillation or the fractional crystallization method are more preferably used. In particular, a wax synthesized by a method not based on alkylene polymerization is preferable from the viewpoint of its molecular weight distribution.

One type of these waxes may be used alone, or two or more types may be used in combination. The wax is preferably added in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

As the toner, a known charge control agent can be used as the charge control agent. Known charge control agents include azo iron compounds, azo chromium compounds, azo manganese compounds, azo cobalt compounds, azo zirconium compounds, chromium compounds of carboxylic acid derivatives, zinc compounds of carboxylic acid derivatives, and carboxylic acid derivatives. Examples of the aluminum compound and the carboxylic acid derivative zirconium compound. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid. A charge control resin can also be used. If necessary, one kind or two or more kinds of charge control agents may be used in combination. The charge control agent is preferably added in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner of the present invention may be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, a normal magnetic carrier such as ferrite or magnetite or a resin coated carrier can be used. Further, a binder type magnetic carrier core in which magnetic powder is dispersed in a resin can also be used.

The resin-coated carrier is composed of magnetic carrier core particles and a resin-coated layer that coats (coats) the surface of the magnetic carrier core particles. Examples of the resin used for the resin coating layer include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; acrylic acid ester copolymers and methacrylic acid ester copolymers. Acrylic resin; Fluorine-containing resin such as polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, monochlorotrifluoroethylene polymer, polyvinylidene fluoride; silicone resin; polyester resin; polyamide resin; polyvinyl butyral; aminoacrylate Resin is mentioned. Other examples include iomonomer resin and polyphenylene sulfide resin. These resins can be used alone or in combination of two or more.

The magnetic carrier in the present invention has magnetic carrier core particles and a resin coating layer formed on the magnetic carrier core particles.
The resin coating layer contains N element, Si element, and F element.
In elemental analysis by X-ray photoelectron spectroscopy
(I) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected by the surface analysis of the magnetic carrier are N1, S1, and F1 (atom%), respectively. )age,
(Ii) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected at a depth of 40 nm from the surface of the magnetic carrier are N2, S2, respectively. When F2 (atomic%)
The N1, S1, F1, N2, S2 and F2
0.1 ≤ N1 ≤ 1.5
0.3 ≤ S1 ≤ 5.0
45.0 ≤ F1 ≤ 65.0
S1 <S2
S1 / N1 <S2 / N2
F1> F2
A magnetic carrier that satisfies the above relationship is preferable.

By using a magnetic carrier within the above range, the chargeability with the toner becomes better and the embossing transferability becomes better.

<Elemental analysis method by X-ray photoelectron spectroscopy of magnetic carriers>
Elemental analysis of magnetic carriers is measured as follows using X-ray photoelectron spectroscopy (XPS). As a measurement sample, a magnetic carrier is set in a sample set hole of φ2 mm and a depth of 2 mm machined on an XPS dedicated platen. Then, the X-ray irradiation site and the sputtering location by GCIB irradiation are set in the sample set hole by the following XPS device.

Equipment used: PHI5000 VersaProbeII manufactured by ULVAC-PHI
Irradiation line: Al-Kα line Beam diameter: 100 μm
Output: 25W15kV
Photoelectron uptake angle: 45 °
Pass Energy: 58.70 eV
Stepsize: 0.125 eV
XPS peaks: F1s, Si2p, N1s, C1s, O1s
Measurement range: 300 μm x 200 μm
Under the above conditions, N1, S1 and F1 (atomic%) were measured.

Further, under the following sputtering conditions, sputtering was performed from the surface of the magnetic carrier to a position at a depth of 40 nm, and the values measured under the above measurement conditions were N2, S2, and F2 (atomic%).

GUN type: GCIB
SputterSetting: 20kV
Regarding the position of the depth of 40 nm, the sputtering rate (rate of the depth with respect to time) is measured in advance, the sputtering time corresponding to 40 nm is calculated, and the sputtering is performed for the corresponding time to obtain the position of the depth of 40 nm. did.

Examples of a method for preferably producing the magnetic carrier of the present invention include a method of spraying a coating resin solution while suspending and flowing the magnetic carrier core particles to form a resin coating layer on the surface of the magnetic carrier core particles, and a spray-drying method. When such a fluidized bed covering device is used, the state of formation of the fluidized bed and the spray type of the resin solution in which the coating resin is dissolved are particularly important. In the state of forming the fluidized bed described above, in order to form the coating layer efficiently without agglutination of the magnetic carrier core particles, a rotary bottom plate disk and a stirring blade are provided in the fluidized bed to form a swirling flow. A method of coating can be mentioned. Specifically, as such a method, (1) a fluidized bed is formed by a gas flow rising in a cylindrical tube, and (2) a coating resin solution is further supplied from a direction perpendicular to the moving direction of the fluidized bed. , (3) and a magnetic carrier manufacturing method characterized in that the spray pressure of the resin solution is 1.5 kg / cm ^{2 or more.}

In the toner of the present invention, it is preferable to externally add silica fine powder to the toner particles in order to improve charge stability, developability, fluidity, and durability. The specific surface area of the silica fine powder by the BET method by nitrogen adsorption ^{is preferably 30 m 2} / g or more and 500 m ² / g or less, and ^{more preferably 50 m 2} / g or more and 400 m ² / g or less. Further, it is preferable to use 0.01 part by mass or more and 8.00 part by mass or less of silica fine powder with respect to 100 parts by mass of toner particles, and more preferably 0.10 part by mass or more and 5.00 parts by mass or less.

The BET specific surface area of the silica fine powder is determined by using, for example, the specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI2360 / 2375 (manufactured by Micrometric), and Tristar 3000 (manufactured by Micrometric). It can be calculated by adsorbing nitrogen gas on the surface of the body and using the BET multipoint method.

The silica fine powder has, if necessary, an unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane coupling agents, and functional groups for the purpose of controlling hydrophobicity and frictional chargeability. It is also preferable that the treatment is performed with a treatment agent such as a silane compound or another organosilicon compound, or in combination with various treatment agents.

Further, other external additives may be added to the toner of the present invention, if necessary. Examples of such an external additive include resin fine particles that act as a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a mold release agent at the time of fixing a thermal roller, a lubricant, an abrasive, and the like. Inorganic fine powder can be mentioned. Examples of the charging aid include metal oxides such as titanium oxide, zinc oxide, and alumina. Examples of the lubricant include polyvinylidene fluoride powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

The method for producing the toner particles in the present invention is not particularly limited, and the toner particles can be produced by a known method. For example, a pulverization method, an emulsification / aggregation method, a suspension polymerization method, a dissolution / suspension method, and the like can be mentioned.

The toner particles produced by the pulverization method are produced, for example, as follows. The binder resin, colorant and other additives, if necessary, are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mixture is melt-kneaded using a heat kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder. At that time, wax, magnetic iron oxide particles and a metal-containing compound can also be added. After the melt-kneaded product is cooled and solidified, it is pulverized and classified to obtain toner particles. At this time, the average circularity of the toner particles can be controlled by adjusting the exhaust temperature at the time of fine pulverization. Further, if necessary, the toner particles and the external additive can be mixed by a mixer such as a Henschel mixer to obtain the toner.

Examples of the mixer include the following. Henschel Mixer (Mitsui Mining Co., Ltd.); Super Mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); Nowter Mixer, Turbulizer, Cyclomix (Hosokawa Micron Co., Ltd.); Spiral Pin Mixer (Pacific Kiko Co., Ltd.) Ladyge mixer (manufactured by Matsubo).

Examples of the kneading machine include the following. KRC kneader (manufactured by Kurimoto Iron Works); Bus co kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Japan Steel Works); Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Mfg. Co., Ltd.); Kneedex (Mitsui Mine Co., Ltd.); MS type pressurized kneader, Nider Ruder (Moriyama Mfg. Co., Ltd.); Banbury mixer (Kobe Steel) Made by Tokorosha).

Examples of the crusher include the following. Counter jet mill, micron jet, innomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries); cross jet mill (manufactured by Kurimoto Iron Works); Ulmax (manufactured by Nippon Soda Engineering Co., Ltd.) ); SK Jet O Mill (manufactured by Seishin Enterprise); Cryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turboe Co., Ltd.); Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

If necessary, after crushing, hybridization system (manufactured by Nara Machinery Co., Ltd.), Nobilta (manufactured by Hosokawa Micron), mechanofusion system (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron), innomizer (manufactured by Hosokawa Micron). , Theta composer (manufactured by Tokuju Kosakusho), Mechanomill (manufactured by Okada Seiko Co., Ltd.), Meteole Invo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) to perform surface treatment of toner particles and control the average circularity of the toner particles. You can also do it.

Examples of the classifier include the following. Classy Classy, Micron Classy Fire, Spedic Classy Fire (manufactured by Seishin Enterprise); Turbo Classy Fire (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (Nittetsu Mining Co., Ltd.); YM Microcut (Yasukawa Shoji Co., Ltd.).

Examples of the sieving device used for sieving the coarse particles include the following. Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonase sieve, gyro shifter (manufactured by Tokuju Kosakusho); Vibrasonic system (manufactured by Dalton); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo screener (manufactured by Turboe Co., Ltd.); Micro shifter (manufactured by Makino Sangyo Co., Ltd.); Circular vibrating sieve.

Next, a method for measuring the particle size distribution of toner particles according to the present invention will be described.

In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.

(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.

(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are placed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the contaminanton N is added into the water tank.

(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.

(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.

(6) The electrolytic aqueous solution (5) in which toner particles are dispersed is dropped onto the (1) round bottom beaker installed in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. Then, the measurement is performed until the number of measurement particles reaches 50,000.

(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

The basic configuration and features of the present invention have been described above, but the present invention will be specifically described below based on examples. However, the present invention is not limited thereto. Unless otherwise specified, parts and% are based on mass.

<Production example of binder resin 1>
-Bisphenol A ethylene oxide (2.2 mol adduct): 50.0 mol parts-Bisphenol A propylene oxide (2.2 mol adduct): 50.0 mol parts-Terephthalic acid: 90.0 mol parts-Trimellitic anhydride Merit acid: 10.0 mol parts 100 parts by mass of the monomer constituting the polyester unit was mixed with 500 ppm of titanium tetrabutoxide into a 5 liter autoclave.

A reflux condenser, a moisture separator, an N ₂ gas introduction pipe, a thermometer and a stirrer were attached thereto, and a depolymerization reaction was carried out at 230 ° C. while introducing _{N 2 gas into the autoclave.} The reaction time was adjusted so as to reach a desired softening point, and after the reaction was completed, the mixture was taken out of the container, cooled, and pulverized to obtain a binder resin 1. The Tm of the binder resin 1 was 130 ° C., and the Tg was 57 ° C.

<Production example of crystalline polyester 1>
・ 50 mol parts of 1,10-decandicarboxylic acid ・ 50 mol parts of ethylene glycol Equipped with 0.2% dibutyltin oxide with respect to the above monomers and the total amount of monomers, nitrogen introduction pipe, dehydration pipe, stirrer and thermocouple It was placed in a 10 L four-necked flask and reacted at 180 ° C. for 4 hours. Then, the temperature was raised to 210 ° C. at 10 ° C./1 hour, the temperature was maintained at 210 ° C. for 8 hours, and then the reaction was carried out at 8.3 kPa for 1 hour to obtain crystalline polyester 1.

<Production example of resin fine particle dispersion liquid 1>
Two parts of sodium dodecyl sulfate and 1600 parts of ion-exchanged water were put into a beaker equipped with a stirrer, and stirring was continued at 25 ° C. until the mixture was completely dissolved to prepare an aqueous medium 1. Then, the following raw materials and 160 parts of toluene were charged in a closed container and heated to 70 ° C. to completely dissolve them to prepare a monomer solution 1.
・ 10 parts of aminoethyl methacrylate ・ 10 parts of cyclohexyl methacrylate ・ 60 parts of styrene ・ 20 parts of methyl methacrylate After lowering the temperature of the above monomer solution 1 to 25 ° C, 6 parts of tertiary butyl peroxypivalate was mixed as a polymerization initiator. The emulsion of the above-mentioned monomer solution 1 was prepared by putting it into the above-mentioned aqueous medium 1 and irradiating it with ultrasonic waves with a high-power ultrasonic homogenizer (VCX-750).

The above emulsion was charged into a heat-dried four-necked flask. After bubbling nitrogen for 30 minutes while stirring the emulsion at 200 rpm, stirring was performed at 75 ° C. for 6 hours. Then, the emulsion was air-cooled in a stirred state to stop the reaction, and a dispersion of coarse particulate resin was obtained.

The fine particle resin and toluene in the dispersion were separated by a centrifuge at 16500 rpm for 2.5 hours.

Then, the supernatant was removed to obtain a dispersion of concentrated resin fine particles.

Then, in a beaker equipped with a stirrer, a dispersion of concentrated resin fine particles was dispersed in acetone using a high-power ultrasonic homogenizer (VCX-750) to obtain a solid content concentration of 10.0% by mass. Resin fine particle dispersion 1 was prepared. The volume average particle diameter of the resin fine particles in the resin fine particle dispersion liquid 1 was 0.20 μm.

<Production example of resin fine particle dispersion liquids 2 to 11>
Resin fine particle dispersions 2 to 11 were obtained in the same manner as in the production example of the resin fine particle dispersion 1 except that the types of monomers other than styrene and the volume average particle diameter were changed as shown in Table 1.

<Example 1>
・ Bundling resin 1 100 parts ・ Crystalline polyester 15 parts ・ Behenic acid behenic acid (melting point 72 ° C) 4 parts ・ C.I. I. Pigment Blue 15:34 4 parts The above materials were premixed with a Henschel mixer and then melt-kneaded at 160 ° C. with a twin-screw kneading extruder.

The obtained kneaded product was cooled, roughly pulverized with a hammer mill, and then finely pulverized with a turbo mill.

The obtained finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1 having a weight average particle diameter (D4) of 6.0 μm.

Subsequently, 300 parts of ion-exchanged water was put into a reaction vessel equipped with a reflux condenser, a stirrer, and a thermometer, and dilute hydrochloric acid was added at 25 ° C. to adjust the pH to 4. Next, 100 parts of the toner particles 1 and the resin fine particle dispersion liquid 1 were gently added so as to have a solid content of 1.0 part, and the mixture was stirred at 200 rpm for 15 minutes. Then, it was heated to 80 ° C. (fixation temperature) using a heating oil bath, and stirring was continued for 1 hour. Then, the dispersion was cooled to 20 ° C., filtered, and washed with ion-exchanged water. Then it was dried and classified.

To 100 parts of the obtained powder, 1.0 part of hydrophobicized silica fine particles (surface treatment with an aminosilane coupling agent, specific surface area by nitrogen adsorption measured by the BET method is 140 m ^{2 /} g) and titanium oxide fine particles. 0.5 part was externally mixed and sieved with a mesh having a mesh size of 150 μm to obtain toner 1.

<Examples 2 to 9, Comparative Examples 1 to 3>
Toners 2 to 9 for Examples, Comparative Examples, in the same manner as in the production example of Toner 1, except that the amount of crystalline polyester, the type and amount of the resin fine particle dispersion liquid, and the fixing temperature were changed as shown in Table 2. Toners 10 to 12 for use were obtained.

<Production example of magnetic carrier core particles>
_{-Fe 2} O ₃ 62.7 parts-MnCO ₃ 29.5 parts-Mg (OH) ₂ 6.8 parts-SrCO ₃ 1.0 parts The ferrite raw materials were weighed so as to have the above composition ratio.

Then, it was pulverized and mixed with a dry vibration mill using stainless beads for 5 hours. 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, and then fine powder was removed with a vibrating sieve having an opening of 0.5 mm. 01% by volume), calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite.

After pulverizing the calcined ferrite to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of the calcined ferrite using zirconia beads, and the mixture was pulverized with a wet ball mill for 1 hour. Further, the obtained slurry was pulverized with a wet ball mill for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

To 100 parts of calcined ferrite, 1.0 part of ammonium polycarboxylic acid as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to the ferrite slurry, and a spray dryer (manufacturer: Okawara Kakoki) was added. ), The particles were granulated into spherical particles. 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.

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, and then firing was performed 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.

After crushing the agglomerated particles, the low magnetic force product is cut by magnetic force beneficiation, sieved with a sieve having a mesh size of 250 μm to remove coarse particles, and the volume-based 50% particle size (D50) is 37.0 μm. Magnetic carrier core particles were obtained.

<Manufacturing example of magnetic carrier 1>
A thermosetting silicone resin solution (methyl silicone resin) is coated with a rotating bottom plate disk and stirring blades in a fluidized bed so that the amount of resin coated is 0.2 with respect to 100 parts of magnetic core particles to form a swirling flow. The magnetic carrier core particles 1 were coated using a coating device for coating while coating. The resin solution described above was sprayed from a direction perpendicular to the moving direction of the fluidized bed in the apparatus. Next, the thermosetting fluororesin solution (FEP) and the thermosetting melamine resin solution were mixed with sufficient stirring so that the solid content ratio was 20 parts: 1 part to prepare a carrier coating solution. Using a coating device that coats this coating solution while forming a swirling flow by providing a rotary bottom plate disk and stirring blades in the fluidized bed, 100 parts of the magnetic carrier core particles are coated with fluororesin and melamine resin. The magnetic core particles were coated so that the total was 2 parts. Then, the obtained carrier was dried in a fluidized bed at a temperature of 280 ° C. for 1 hour to remove the solvent, and then a magnetic carrier 1 was obtained.

Elemental analysis of the obtained carriers by X-ray photoelectron spectroscopy revealed that N1 was 0.4, S1 was 0.7, F1 was 57.6, N2 was 0.3, and S2 was 1.6. , F2 was 56.7.

<Manufacturing example of magnetic carrier 2>
A thermosetting silicone resin solution (methyl silicone resin) is coated by providing a rotary bottom plate disk and stirring blades in the fluidized floor so that the amount of resin is 3 parts with respect to 100 parts of magnetic core particles to form a swirling flow. The above-mentioned magnetic core particles 1 were coated using a coating device for performing the above. The resin solution described above was sprayed from a direction perpendicular to the moving direction of the fluidized bed in the apparatus. Then, the obtained carrier was dried in a fluidized bed at a temperature of 280 ° C. for 1 hour to remove the solvent, and then a magnetic carrier 2 was obtained. Elemental analysis of the obtained carriers by X-ray photoelectron spectroscopy revealed that N1 was 0, S1 was 54.3, F1 was 0, N2 was 0, S2 was 54.0, and F1 was 0. ..

<Preparation and evaluation of two-component developer 1>
^{0.5s -1 of} toner 1 and magnetic carrier 1 using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the amount of toner 1 is 10 parts with respect to 90 parts of magnetic carriers. , The two-component developer 1 was prepared by mixing under the condition of a rotation time of 5 min. The following evaluation was performed using the obtained developer 1. The evaluation results are shown in Table 3.

<Evaluation>
An imagePRESS C800 (manufactured by Canon) was used as an image forming apparatus, and the developer carrier was modified so that the DC voltage VDC and transfer current could be freely set. The two-component developer 1 is placed in the developer at the cyan position of this modified machine, and the charging voltage VD and laser power of the electrostatic latent image carrier are adjusted so that the amount of toner loaded on the paper becomes desired, and the evaluation described later is performed. Was done.

<Evaluation of embossed transferability>
Paper: Rezac 66 250g A4 size paper Toner load on paper: 0.90mg / cm ²
Evaluation image: Solid image Obtaining the above image while changing the transfer current value, using a scanner (trade name: CanoScan 9000F, manufactured by Canon Corporation), reading resolution 600 dpi, image correction processing OFF. The JPG image was read, and the density histogram of the entire surface of the image was measured with ImageJ, and the standard deviation was obtained. Ranking was performed according to the following evaluation criteria according to the value of the standard deviation in the transfer current value at which the standard deviation is the minimum value.

(Evaluation criteria)
A: Standard deviation less than 10 B: Standard deviation 10 or more and less than 12 C: Standard deviation 12 or more and less than 14 D: Standard deviation 14 or more and less than 16 E: Standard deviation 16 or more <Scratch resistance>
Paper: OK Top Coat +, Oji Paper, 127g / m ²
Evaluation image: Halftone image (image density: 0.20 or more and 0.25 or less)
The image density is measured by using the "Macbeth Reflection Densitometer RD918" (manufactured by Macbeth) and measuring the relative density of the white background with an image density of 0.00 according to the attached instruction manual. , The obtained relative density was used as the value of the image density.

Paper (OK top coat +, made by Oji Paper, 127 g / m ² ) is placed on the above image sample, and a weight of 500 g is placed on it so that the ground contact area is 12.6 cm ^{2 10 times.} A scratch resistance test was performed. Then, the toner adhering to the area of 12.6 cm ² of the paper (the area on which the weight was placed) was measured with a fog meter, and the obtained fog value was evaluated according to the following criteria.

(Evaluation criteria)
A: Fog is 2% or less B: Fog is 2% or more and less than 5% C: Fog is 5% or more and less than 10% D: Fog is 10% or more and less than 15% E: Fog is 15% or more <Two-component developer 2 Preparation and evaluation of ~ 9>
Two-component developing agents 2 to 9 were obtained in the same manner as in the preparation of the two-component developing agent 1 except that the toner and the magnetic carrier were changed as shown in Table 3. Further, the evaluation was carried out in the same manner as in the two-component developer 1. The evaluation results are shown in Table 3.

<Preparation and evaluation of two-component developing agents 10 to 12>
Two-component developeres 10 to 12 were obtained in the same manner as in the preparation of the two-component developer 1 except that the toner and the magnetic carrier were changed as shown in Table 4. Further, the evaluation was carried out in the same manner as in the two-component developer 1. The evaluation results are shown in Table 4.

Claims (7)

Toner particles having a binder resin and toner particles having resin fine particles.
The resin fine particles are vinyl-based resin fine particles.
The vinyl-based resin has a cycloalkyl (meth) acrylate unit and a nitrogen-containing vinyl-based monomer unit in one molecule.
The nitrogen-containing vinyl-based monomer unit includes an amino group, an amide group, an imide group, a urethane bond, a urea bond, a monovalent functional group formed by removing one hydrogen atom from the nitrogen-containing heterocyclic compound, and a monovalent functional group. It has at least one functional group selected from the group consisting of quaternary ammonium bases.
Toner characterized by that. The toner according to claim 1, wherein the volume average particle diameter of the resin fine particles is 0.05 μm or more and 0.50 μm or less. The toner according to claim 1 or 2, wherein the content of the resin fine particles is 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. The toner according to any one of claims 1 to 3, wherein the resin fine particles contain the nitrogen-containing vinyl-based monomer unit in an amount of 1% by mass or more and 20% by mass or less. The toner according to any one of claims 1 to 4, wherein the adhesion rate of the resin fine particles to the toner particles is 50% or more. The toner according to any one of claims 1 to 5, wherein the toner particles contain crystalline polyester. A two-component developer containing toner and a magnetic carrier.
The toner is the toner according to any one of claims 1 to 6.
The magnetic carrier has magnetic carrier core particles and a resin coating layer formed on the magnetic carrier core particles.
The resin coating layer contains N element, Si element, and F element.
In elemental analysis by X-ray photoelectron spectroscopy
(I) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected by the surface analysis of the magnetic carrier are N1, S1, and F1 (atom%), respectively. )age,
(Ii) The ratios of N atoms, Si atoms, and F atoms to the total sum of N atoms, Si atoms, F atoms, C atoms, and O atoms detected at a depth of 40 nm from the surface of the magnetic carrier are N2, S2, respectively. When F2 (atomic%)
The N1, S1, F1, N2, S2 and F2
0.1 ≤ N1 ≤ 1.5
0.3 ≤ S1 ≤ 5.0
45.0 ≤ F1 ≤ 65.0
S1 <S2
S1 / N1 <S2 / N2
F1> F2
A two-component developer characterized by satisfying the relationship of.