JP2014153661A - Toner set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner set having excellent low-temperature fixability and heat-resistant storage stability, and capable of forming solid images with good granularity.SOLUTION: A toner set according to an embodiment of the present invention includes a clear toner and a colored toner. The clear toner includes a binder resin and a mold release agent, and the colored toner includes a binder resin, a pigment, and a mold release agent. When a volume average particle diameter of the clear toner is A[μm], and a volume average particle diameter of the colored toner is B[μm], the formula 4.8≤A≤8.41.0<A/B≤1.2 is satisfied.

Description

  One embodiment of the present invention relates to a toner set, a developer set, and an image forming apparatus.

  In electrophotography, an electrostatic latent image is formed on a photoconductor, and then the electrostatic latent image is developed with toner to form a visualized toner image.

  A method of forming a toner image on a recording medium using clear toner and colored toner is known.

  However, there is a problem that the low-temperature fixability and the heat-resistant storage stability of the clear toner cannot be compatible.

  Patent Document 1 discloses an image forming apparatus that performs fixing after superposing a white toner image and a color toner image formed on an image carrier on a transfer material. At this time, the volume average particle size of the white toner used for forming the white toner image is 1.3 to 2.0 times the volume average particle size of the color toner used for forming the color toner image.

  However, there is a problem that the granularity of the solid image is lowered.

  One embodiment of the present invention is to provide a toner set capable of forming a solid image having excellent low-temperature fixability and heat-resistant storage stability and excellent granularity, in view of the above-described problems of the prior art. .

One embodiment of the present invention includes a clear toner and a color toner in a toner set, and the clear toner includes a binder resin and a release agent, and the color toner includes a binder resin, a pigment, and a release agent. And the volume average particle diameter of the clear toner is B [μm] and the volume average particle diameter of the colored toner is B [μm], the formula 4.8 ≦ A ≦ 8.4
1.0 <A / B ≦ 1.2
Meet.

  According to an embodiment of the present invention, it is possible to provide a toner set capable of forming a solid image having excellent low-temperature fixability and heat-resistant storage stability and excellent granularity.

It is an evaluation chart of granularity. It is a threshold value matrix of halftone processing A.

  Next, the form for implementing this invention is demonstrated.

  The toner set includes clear toner and colored toner. At this time, the clear toner includes a binder resin and a release agent, and the colored toner includes a binder resin, a pigment, and a release agent.

Assuming that the volume average particle diameter of the clear toner is A [μm] and the volume average particle diameter of the colored toner is B [μm], the formula 4.8 ≦ A ≦ 8.4
1.0 <A / B ≦ 1.2
Is satisfied and the formula 5.4 ≦ A ≦ 7.2 is satisfied.
1.05 ≦ A / B ≦ 1.20
It is preferable to satisfy.

  If A is less than 4.8, the low-temperature fixability and heat-resistant storage stability of the clear toner cannot be achieved at the same time, and the granularity of the solid image decreases. If it exceeds 8.4, the granularity of the solid image is low. descend.

  If A / B is 1.0 or less, the low-temperature fixability and heat-resistant storage stability of the clear toner cannot be compatible, and if it exceeds 1.2, the granularity of the solid image is lowered.

  The reason why the low-temperature fixability and the heat-resistant storage stability of the clear toner cannot be achieved is considered to be because it does not contain a pigment. Colored toners are estimated to be able to achieve both low-temperature fixability and heat-resistant storage stability because the hardness of the colored toner is improved by the filler effect of the pigment, or the presence of the pigment on the surface improves the hardness of the surface. The

  The volume average particle diameter of the clear toner and the colored toner can be measured by a Coulter method.

  The clear toner and the color toner preferably contain crystalline polyester.

  The crystalline polyester in the clear toner and the colored toner exhibits a heat-melting characteristic in which the viscosity rapidly decreases near the fixing start temperature. In other words, the toner is excellent in heat-resistant storage stability immediately before the melting start temperature, and the viscosity is rapidly lowered and fixed at the melting start temperature, so that a toner excellent in heat-resistant storage stability and low-temperature fixing property can be designed. Further, the release width, that is, the difference between the fixing lower limit temperature and the hot offset occurrence temperature also increases.

  Although it does not specifically limit as an alcohol component used when synthesize | combining crystalline polyester, C2-C12 saturated aliphatic diol compound (For example, 1, 4- butanediol, 1, 6-hexanediol, 1 , 8-octanediol, 1,10-decanediol, 1,12-dodecanediol) or derivatives thereof.

  Although it does not specifically limit as an acidic component used when synthesize | combining crystalline polyester, C2-C12 dicarboxylic acid (for example, fumaric acid) which has a carbon-carbon double bond, C2-C12 Of saturated dicarboxylic acids (for example, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid) or these Derivatives.

  The crystalline polyester has high crystallinity, and its viscosity changes rapidly in the vicinity of the melting point, so that 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, A constituent unit derived from a saturated diol component having 4 to 12 carbon atoms of 1,12-dodecanediol, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, It is preferable that any one of 1,10-decanedioic acid and 1,12-dodecanedioic acid has a structural unit derived from a saturated dicarboxylic acid component having 4 to 12 carbon atoms.

  As a method for controlling the crystallinity and softening point of the crystalline polyester, a trivalent or higher polyhydric alcohol such as glycerin is added to the alcohol component during synthesis, or a trivalent or higher trivalent acid such as trimellitic anhydride is added to the acid component. Examples include a method of adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement using a solution or solid, but for convenience, it is 965 ± in the infrared absorption spectrum. It can be confirmed by absorption based on δCH (out-of-plane variable angular vibration) of olefin of 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ .

  The crystalline polyester preferably has a weight average molecular weight of 5000 to 20000 of components soluble in o-dichlorobenzene. When the weight average molecular weight of the component soluble in o-dichlorobenzene of the crystalline polyester is less than 5000, the heat-resistant storage stability of the clear toner and the color toner may be deteriorated, and when it exceeds 20000, the clear toner and the color toner The low-temperature fixability of the ink may deteriorate.

  In the crystalline polyester, the ratio of the molecular weight of 500 or less is preferably 2% or less, and the ratio of the molecular weight of 1000 or less is preferably 4% or less. Thereby, the heat-resistant storage stability of clear toner and colored toner can be improved.

  The molecular weight of the crystalline polyester is a molecular weight in terms of polystyrene measured using GPC.

  The content of the crystalline polyester in the clear toner is preferably 5 to 20% by mass. When the content of the crystalline polyester in the clear toner is less than 5% by mass, the low-temperature fixability of the toner may be lowered, and when it exceeds 20% by mass, the heat-resistant storage stability of the toner may be lowered.

  The content of the crystalline polyester in the clear toner is preferably not less than the content of the crystalline polyester in the colored toner. Thereby, the fixability of a solid image can be improved.

  Although it does not specifically limit as binder resin, Amorphous polyester-type resin etc. are mentioned.

  The binder resin preferably includes a polyester having a crosslinked structure and an amorphous polyester not having a crosslinked structure.

  The polyester having a crosslinked structure can be synthesized by reacting a polyester prepolymer having a group capable of reacting with an active hydrogen group and a compound having an active hydrogen group.

  Polyester with a cross-linked structure makes it easy to adjust the molecular weight of the polymer component and ensures oil-free low-temperature fixing characteristics, especially good release and fixing properties even when there is no release oil application mechanism to the fixing heating medium. In view of the ability, it is preferably a urea-modified amorphous polyester.

  The group capable of reacting with an active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, an epoxy group, a carboxyl group, and an acid chloride group, and two or more kinds may be used in combination.

  The polyester prepolymer having a group capable of reacting with an active hydrogen group is not particularly limited, but a polyester prepolymer (A) having an isocyanate group is preferable in that a urea-modified amorphous polyester can be synthesized.

  The polyester prepolymer (A) having an isocyanate group is synthesized by reacting a non-crystalline polyester having a hydroxyl group, which is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), with a polyisocyanate (PIC). Can do.

  Although it does not specifically limit as a polyol (PO), A diol (DIO), a trihydric or more polyol (TO), a mixture of a diol (DIO) and a trihydric or more polyol (TO), etc. are mentioned, 2 or more types combined use May be. Among these, diol (DIO) or a mixture of diol (DIO) and a small amount of a trivalent or higher polyol (TO) is preferable.

  Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.

  Examples of the alkylene glycol include compounds having 2 to 12 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

  Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.

  Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  Examples of the alkylene oxide adduct of alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to alicyclic diol.

  Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S.

  Examples of the alkylene oxide adduct of bisphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols.

  Among them, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and alkylene oxide adducts of bisphenols, mixtures of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Further preferred.

  Examples of the trivalent or higher polyol (TO) include trivalent or higher polyhydric aliphatic alcohols, trivalent or higher polyphenols, and alkylene oxide adducts of trivalent or higher polyphenols.

  Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.

  Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like.

  Examples of the alkylene oxide adduct of a trihydric or higher polyphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to a trihydric or higher polyphenol.

  The mixing mass ratio of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is usually 100: 0.01 to 10, and 100: It is preferable that it is 0.01-1.

  The polycarboxylic acid (PC) is not particularly limited, and examples thereof include dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid, and the like. Two or more kinds may be used in combination. Of these, dicarboxylic acid (DIC) or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

  Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, and aromatic dicarboxylic acid.

  Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid and the like.

  Examples of the alkenylene dicarboxylic acid include compounds having 4 to 20 carbon atoms such as maleic acid and fumaric acid.

  Examples of the aromatic dicarboxylic acid include compounds having 8 to 20 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

  Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  Examples of the trivalent or higher polycarboxylic acid (TO) include aromatic polycarboxylic acid.

  Examples of the aromatic polycarboxylic acid include compounds having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid.

  In place of polycarboxylic acid (PC), an acid anhydride or lower alkyl ester of polycarboxylic acid (PC) can also be used.

  Although it does not specifically limit as a lower alkyl ester, Methyl ester, ethyl ester, isopropyl ester etc. are mentioned.

  The mixing mass ratio of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) is usually 100: 0.01 to 10 It is preferable that it is 100: 0.01-1.

  Equivalent ratio ([OH] / [COOH) of hydroxyl group [OH] of polyol (PO) and carboxyl group [COOH] of polycarboxylic acid (PC) at the time of polycondensation of polyol (PO) and polycarboxylic acid (PC) ]) Is usually 1 to 2, preferably 1 to 1.5, and more preferably 1.02 to 1.3.

  The content of the structural unit derived from the polyol (PO) in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, More preferably, it is 20 mass%. When the content of the structural unit derived from the polyol (PO) in the polyester prepolymer (A) having an isocyanate group is less than 0.5% by mass, the heat-resistant storage stability of the clear toner and the colored toner may be lowered. If it exceeds 40% by mass, the low-temperature fixability of the clear toner and the color toner may be lowered.

  Although it does not specifically limit as polyisocyanate (PIC), Aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates, etc. are mentioned, You may use 2 or more types together.

  Aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane. Diisocyanate etc. are mentioned.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.

  As aromatic diisocyanates, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3-methyldiphenylmethane— 4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, and the like.

  Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.

  Examples of isocyanurates include tris (isocyanatoalkyl) isocyanurate and triisocyanatocycloalkyl isocyanurate.

  In place of polyisocyanate (PIC), the isocyanate group of polyisocyanate (PIC) blocked with a phenol derivative, oxime, caprolactam or the like may be used.

  Polyisocyanate (PIC) and the isocyanate group [NCO] of the polyisocyanate (PIC) when the amorphous polyester having a hydroxyl group is reacted with the hydroxyl group [OH] of the amorphous polyester having a hydroxyl group ([ NCO] / [OH]) is usually from 1 to 5, preferably from 1.2 to 4, more preferably from 1.5 to 3. When the mixing equivalent ratio ([NCO] / [OH]) is less than 1, the heat-resistant storage stability of the clear toner and the color toner may be deteriorated. When it exceeds 5, the low temperature fixability of the clear toner and the color toner is decreased. May decrease.

  The content of the structural unit derived from polyisocyanate (PIC) in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, preferably 2 More preferably, it is -20 mass%. When the content of the structural unit derived from polyisocyanate (PIC) in the polyester prepolymer (A) having an isocyanate group is less than 0.5% by mass, the heat-resistant storage stability of the clear toner and the colored toner may be lowered. If it exceeds 40 mass%, the low-temperature fixability of the clear toner and the color toner may be lowered.

  The average value of the number of isocyanate groups contained in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.2 to 5, and more preferably 1.5 to 4. When the average value of the number of isocyanate groups contained in the polyester prepolymer (A) having an isocyanate group is less than 1, the heat resistant storage stability of the clear toner and the colored toner may be lowered.

Although it does not specifically limit as a specific example of the synthesis method of the polyester prepolymer (A) which has an isocyanate group, The following method is mentioned.
(1) Method of reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with isophorone diisocyanate (2) Reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with isophorone diisocyanate (3) Method of reacting bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate (4) Ethylene oxide 2 mol adduct of bisphenol A , A method of reacting bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate (5) bisphenol A ethylene oxide 2 mol adduct and terephthal Method of reacting acid polycondensate with isophorone diisocyanate (6) Method of reacting bisphenol A ethylene oxide 2-mole adduct and terephthalic acid polycondensate with isophorone diisocyanate (7) Ethylene oxide 2-mole adduct of bisphenol A And a method of reacting a polycondensate of terephthalic acid with isophorone diisocyanate (8) A method of reacting an adduct of bisphenol A with ethylene oxide 2 mol and a polycondensate of isophthalic acid with diphenylmethane diisocyanate (9) 2 mol of ethylene oxide of bisphenol A Method of reacting adduct, polycondensate of bisphenol A propylene oxide 2 mol, terephthalic acid and dodecenyl succinic anhydride with diphenylmethane diisocyanate (10) Bisphenol Method of reacting 2-condensate of ethylene oxide with polycondensate of isophthalic acid with toluene diisocyanate The active hydrogen group is not particularly limited, but is a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group, carboxyl group, mercapto Group etc. are mentioned and you may use 2 or more types together.

  The compound having an active hydrogen group is not particularly limited, but amines (B) are preferable in that a urea-modified amorphous polyester can be synthesized.

  Examples of amines (B) include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and the like. Good. Of these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are preferable.

  Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines.

  Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like.

  Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine.

  Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

  Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.

  Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.

  Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  In addition, you may use what blocked the amino group of amines (B) instead of amines (B).

  As what blocked the amino group of amines (B), the ketimine obtained from amines (B) and ketones (Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an oxazolyson, etc. are mentioned.

  In addition, in order to stop reaction of the amorphous polyester prepolymer (A) which has an isocyanate group, and amines (B), a reaction terminator can be used. Thereby, the molecular weight and the like of the binder resin can be controlled within a desired range.

  Although it does not specifically limit as a reaction terminator, For example, monoamine (For example, diethylamine, dibutylamine, butylamine, laurylamine) etc. are mentioned.

  In addition, you may use what blocked the amino group of monoamine instead of monoamine.

  The mixing equivalent ratio ([NCO] / [NHx]) of the isocyanate group [NCO] in the amorphous polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amines (B) is usually 1/3 to 3, preferably 1/2 to 2, and more preferably 2/3 to 3/2. When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low temperature fixability of the clear toner and the color toner may be deteriorated. May decrease.

  An amorphous polyester having no cross-linked structure can be synthesized by polycondensation of the aforementioned polyol (PO) and polycarboxylic acid (PC).

  The release agent preferably has a melting point of 70 to 90 ° C. Since such a release agent can effectively act at the interface between the fixing roller and the toner, hot offset resistance can be improved without applying a release agent such as oil to the fixing roller. .

  Although it does not specifically limit as a mold release agent, Plant waxes, such as carnauba wax, cotton wax, a wood wax, rice wax, animal waxes, such as beeswax, lanolin; Mineral waxes, such as ozokerite and cercin, paraffin, microcrystalline , Natural wax such as petroleum wax such as petrolatum; synthetic hydrocarbon wax such as Fischer-Tropsch wax and polyethylene wax, synthetic wax such as ester, ketone and ether; 1,2-hydroxystearic amide, stearic amide, phthalic anhydride Fatty acid amides such as acid imides; long side chains of acrylate homopolymers such as poly (n-stearyl methacrylate) and poly (n-lauryl methacrylate), and acrylate copolymers such as n-stearyl acrylate-ethyl methacrylate copolymers Crystalline polymers of low molecular weight having an alkyl group. Of these, hydrocarbon waxes or ester waxes are preferred.

  The release agent contained in the colored toner is preferably the same as the release agent contained in the clear toner.

  The content of the release agent in the clear toner and the color toner is usually 40% by mass or less, and preferably 3 to 30% by mass. When the content of the release agent in the clear toner and the color toner exceeds 40% by mass, the fluidity of the clear toner and the color toner may be lowered.

  The content of the release agent in the clear toner is preferably not less than the content of the release agent in the color toner. Thereby, the fixability of a solid image can be improved.

  Although it does not specifically limit as a pigment, A magenta pigment, a cyan pigment, a yellow pigment, etc. are mentioned.

  Examples of magenta pigments include 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, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 269, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of cyan pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 etc. are mentioned.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 185, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.

  The pigment may be used alone or in combination with a dye.

  Examples of magenta dyes include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, 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, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 are listed.

  The mass ratio of the colorant to the binder resin is usually 0.03 to 0.2, and preferably 0.04 to 0.15.

  The clear toner preferably further contains a charge control agent.

  The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salt)), alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based surfactant, salicylic acid metal salt, salicylic acid derivative metal salt, copper phthalocyanine, perylene, quinacridone, azo pigment, sulfonic acid group And polymer compounds having a carboxyl group, a quaternary ammonium base, and the like.

  Commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal Complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (made by Nippon Carlit Co., Ltd.).

  The mass ratio of the charge control agent to the binder resin is usually 0.001 to 0.1, and preferably 0.002 to 0.05. If the mass ratio of the charge control agent to the binder resin exceeds 0.1, the electrostatic attractive force of the clear toner with the developing roller may increase and the fluidity may decrease.

  The charge control agent may be a master batch melt-kneaded with the resin.

  The clear toner and the color toner may further contain a fluidity improver, a cleaning property improver, and a magnetic material.

  The fluidity improver is not particularly limited, but silica particles, alumina particles, titanium oxide particles, barium titanate particles, magnesium titanate particles, calcium titanate particles, strontium titanate particles, zinc oxide particles, tin oxide particles, Silica sand particles, clay particles, mica particles, wollastonite particles, diatomaceous earth particles, chromium oxide particles, cerium oxide particles, bengara particles, antimony trioxide particles, magnesium oxide particles, zirconium oxide particles, barium sulfate particles, barium carbonate particles , Calcium carbonate particles, silicon carbide particles, silicon nitride particles and the like.

  The average primary particle size of the fluidity improver is usually 5 nm to 2 μm, and preferably 5 to 500 nm.

The specific surface area according to the BET method of the fluidity improver is usually 20 to 500 m ² / g.

  The content of the fluidity improver in the clear toner and the colored toner is usually from 0.01 to 5% by mass, and preferably from 0.01 to 2% by mass. When the content of the fluidity improver in the clear toner and the color toner exceeds 5% by mass, the low-temperature fixability may be lowered.

  The fluidity improver may be hydrophobized with a surface treatment agent.

  The surface treatment agent is not particularly limited, but includes a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone. An oil etc. are mentioned.

  The cleaning property improver is not particularly limited, and examples thereof include fatty acid metal salts such as zinc stearate and calcium stearate, resin particles produced by soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles.

  The volume average particle size of the resin particles is usually from 0.01 to 1 μm, and it is preferable that the particle size distribution is narrow.

  Although it does not specifically limit as a magnetic material, Iron, magnetite, a ferrite, etc. are mentioned.

  The production method of the clear toner and the colored toner is not particularly limited, and examples thereof include a kneading / pulverizing method, a polymerization method, a dissolution suspension method, and a spray granulation method.

  Examples of the polymerization method include an ester elongation polymerization method and an emulsion aggregation fusion method.

  Note that when the clear toner and the colored toner contain crystalline polyester, annealing is required depending on the production method.

  Annealing is an operation for changing the state in which the crystalline polyester and the amorphous polyester are compatible to the incompatible state.

  Hereinafter, the ester extension polymerization method will be described.

  The ester extension polymerization method is not particularly limited, but a group capable of reacting (pigment), a release agent, a crystalline polyester, an amorphous polyester having no cross-linked structure, and an active hydrogen group in an organic solvent. After dissolving or dispersing the toner composition containing the polyester prepolymer having an organic solvent, the organic solvent is removed from the dispersion in which the oil phase in which the compound having an active hydrogen group is dissolved is dispersed in an aqueous medium to obtain base particles. The manufacturing method etc. are mentioned. At this time, the polyester prepolymer having a group capable of reacting with an active hydrogen group reacts with the compound having an active hydrogen group while or after the oil phase is dispersed in an aqueous medium.

  In addition, after dispersing the oil phase which does not contain the compound which has an active hydrogen group in an aqueous medium, you may add the compound which has an active hydrogen group. In this case, the modified polyester is preferentially generated on the surface of the base particle, and a concentration gradient of the modified polyester can be provided inside the base particle.

  The organic solvent is preferably volatile with a boiling point of less than 100 ° C. because it is easy to remove.

  The organic solvent is not particularly limited, but toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples thereof include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone, and two or more kinds may be used in combination. Of these, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.

  The mass ratio of the organic solvent to the resin component is usually 3 or less, preferably 1 or less, and more preferably 0.25 to 0.7.

  The aqueous medium may be water alone, or a solvent miscible with water may be used in combination.

  Solvents miscible with water are not particularly limited, but alcohols (eg, methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolve (eg, methyl cellosolve), lower ketones (eg, acetone, methyl ethyl ketone), and the like. Can be mentioned.

  The materials constituting the toner composition may be mixed when dispersed in an aqueous medium.

  Further, the materials constituting the toner composition do not necessarily need to be mixed when dispersed in the aqueous medium, and may be added after forming the base particles. For example, a colored toner can be produced by forming base particles and then adding a dye by a known dyeing method.

  The disperser used for dispersion in the aqueous medium is not particularly limited, and examples thereof include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. . Especially, since the particle size of a dispersion liquid can be 2-20 micrometers, a high-speed shearing type disperser is preferable.

  The rotational speed of the high-speed shearing disperser is usually 1000 to 30000 rpm, and preferably 5000 to 20000 rpm.

  In the case of a batch method, the time for dispersing using a high-speed shearing disperser is usually 0.1 to 60 minutes.

  The temperature for dispersion using a high-speed shearing disperser is usually from 0 to 80 ° C. (under pressure), and preferably from 10 to 40 ° C.

  The mass ratio of the aqueous medium to the toner composition is usually 1-10. If the mass ratio of the aqueous medium to the toner composition is less than 1, the dispersion state of the toner composition may be lowered, and base particles having a predetermined particle size may not be produced.

  The aqueous medium preferably contains a dispersant. Thereby, the particle size distribution of the dispersion can be sharpened and stably dispersed.

  The dispersant is not particularly limited, but anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amines such as imidazoline. Cationic surfactants of quaternary ammonium salts such as salt-type cationic surfactants, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride Agents, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives, alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium Amphoteric surfactants such as the tines and the like. Among these, a surfactant having a fluoroalkyl group is preferable in that the effect can be obtained with a very small amount.

  Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctane Sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. .

  Commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC. -129 (above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812 F-833 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ectop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products, Inc.) ), And Fgentent F-100, F-150 (manufactured by Neos).

  Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary, or secondary amine acids having a fluoroalkyl group, and aliphatic 4 such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt. Examples include quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Commercially available cationic surfactants having a fluoroalkyl group include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Kogyo Co., Ltd.), Mega Fuck F-150, F-824 (manufactured by Dainippon Ink and Chemicals, Inc.), Xtop EF-132 (manufactured by Tochem Products Co., Ltd.), and Footgent F-300 (manufactured by Neos).

  As the dispersant, inorganic particles that are hardly soluble in water and resin particles that are insoluble in water may be used.

  The inorganic particles hardly soluble in water are not particularly limited, and examples thereof include tricalcium phosphate particles, calcium carbonate particles, titanium oxide particles, colloidal silica, and hydroxyapatite particles.

  The resin particles insoluble in water are not particularly limited, but acids (for example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride) Acid), hydroxyl-containing (meth) acrylic monomers (for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-acrylate) -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate , Glycerin monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide), ethers of vinyl alcohol (eg, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether), esters of compounds containing vinyl alcohol and carboxyl groups (For example, vinyl acetate, vinyl propionate, vinyl butyrate), acrylamide, methacrylamide, diacetone acrylamide or methylolated products thereof, acid chloride (for example, acrylic acid chloride, methacrylic acid chloride), nitrogen atom or heterocyclic ring thereof Homopolymers or copolymers such as monomers (for example, vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine), polyoxyethylene polymers (for example, polyoxyethylene) Ethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester , Polyoxyethylene nonylphenyl ester), celluloses (for example, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose) and the like.

  In addition, when using the compound which melt | dissolves in acids or alkalis, such as calcium phosphate, as a dispersing agent, after dissolving a dispersing agent using acids or alkalis, such as hydrochloric acid, a dispersing agent can be removed by the method of washing with water. it can.

  The dispersant can also be removed by enzymatic degradation.

  When the aqueous medium contains a dispersant, it can be used with the dispersant remaining on the surface of the base particles. However, the dispersant can be removed by washing in terms of the chargeability of the clear toner and the colored toner. preferable.

  The time for reacting the polyester prepolymer having a group capable of reacting with an active hydrogen group and the compound having an active hydrogen group is usually 10 minutes to 40 hours, and preferably 30 minutes to 24 hours. .

  The temperature at which the polyester prepolymer having a group capable of reacting with an active hydrogen group and the compound having an active hydrogen group are reacted is usually 0 to 100 ° C, and preferably 10 to 50 ° C.

  When reacting the polyester prepolymer having a group capable of reacting with an active hydrogen group and the compound having an active hydrogen group, a catalyst may be used as necessary.

  Although it does not specifically limit as a catalyst, Tertiary amines, such as a triethylamine, Imidazole etc. are mentioned.

  The method for removing the organic solvent is not particularly limited, but a method of gradually raising the temperature of the dispersion to evaporate the organic solvent, spraying the dispersion into a dry atmosphere, and evaporating the aqueous medium together with the organic solvent. And the like.

  Although it does not specifically limit as dry atmosphere, Heating gas, such as air, nitrogen, a carbon dioxide gas, combustion gas, is mentioned. Among these, various airflows heated to a temperature equal to or higher than the boiling point of the solvent having the highest boiling point contained in the dispersion are preferable.

  Although it does not specifically limit as a spray dryer used when spraying a dispersion liquid in dry atmosphere, A spray dryer, a belt dryer, a rotary kiln etc. are mentioned.

  After removing the organic solvent, classification may be performed as necessary.

  At this time, fine particles may be removed from the dispersion liquid from which the organic solvent has been removed by cyclone, decanter, centrifugation, or the like, and coarse particles may be removed after the dispersion liquid from which the organic solvent has been removed is dried.

  By mixing the base particles with dissimilar particles such as pigments, mold release agents, charge control agents, fluidity improvers, cleaning improvers, magnetic materials, etc., and applying mechanical impact force to the mixture as necessary The foreign particles may be fixed on the surface of the base particles.

  The method of applying a mechanical impact force to the mixture is not particularly limited, but is a method of applying an impact force to the mixture with a blade rotating at high speed. For example, there is a method of causing the particles to collide with the collision plate.

  As a device for applying a mechanical impact force to the mixture, an ong mill (made by Hosokawa Micron), an I-type mill (made by Nippon Pneumatic Co., Ltd.) was modified to reduce the pulverization air pressure, and a hybridization system (Nara). Machine Seisakusho), Kryptron System (Kawasaki Heavy Industries), automatic mortar, etc.

  The developer set includes the toner set described above, and may further include a carrier. That is, the developer set may be a one-component developer set or a two-component developer set. At this time, the two-component developer set includes a clear two-component developer including a clear toner and a carrier, and a colored two-component developer including a color toner and a carrier.

  The carrier preferably has a core material covered with a resin layer.

  The material constituting the core material is not particularly limited, and examples thereof include a manganese-strontium (Mn—Sr) material and a manganese-magnesium (Mn—Mg) material having a mass magnetization of 50 to 90 emu / g. Two or more species may be used in combination. Among these, from the viewpoint of ensuring image density, a highly magnetized material such as iron having a mass magnetization of 100 emu / g or more and magnetite having a mass magnetization of 75 to 120 emu / g is preferable. Further, the copper-zinc (Cu-Zn) having a mass magnetization of 30 to 80 emu / g is advantageous in that it can weaken the contact of the clear toner and the colored toner with the spiked photoconductor, which is advantageous for high image quality. ) Weakly magnetized materials such as system materials are preferred.

  The volume-based median diameter of the core material is usually 10 to 150 μm, and preferably 40 to 100 μm. If the volume-based median diameter of the core material is less than 10 μm, carrier scattering may occur, and if it exceeds 150 μm, toner scattering may occur.

  The resin constituting the resin layer is not particularly limited, but amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, poly Trifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, terpolymer of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Examples thereof include fluoroterpolymers such as polymers, silicone resins, and the like, and two or more kinds may be used in combination.

  Examples of amino resins include urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins.

  Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral.

  Examples of the polystyrene resin include polystyrene and styrene acrylic copolymer.

  Examples of the halogenated olefin resin include polyvinyl chloride.

  Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

  The resin layer may further contain conductive powder.

  The conductive powder is not particularly limited, and examples thereof include metal powder, carbon black, titanium oxide powder, tin oxide powder, and zinc oxide powder.

  The average particle size of the conductive powder is usually 1 μm or less. When the average particle size of the conductive powder exceeds 1 μm, it may be difficult to control the electric resistance.

  The resin layer can be formed by applying a coating solution in which a resin is dissolved in an organic solvent to the surface of the core material, drying it, and baking it.

  Although it does not specifically limit as an organic solvent, Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

  The method for applying the coating solution is not particularly limited, and examples thereof include a dip coating method, a spray method, and a brush coating method.

  The baking method may be an external heating method or an internal heating method.

  The baking method is not particularly limited, and examples thereof include a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, and a method using a microwave.

  The content of the resin layer in the carrier is usually 0.01 to 5.0% by mass. When the content of the resin layer in the carrier is less than 0.01% by mass, the resin layer may not be uniformly formed on the surface of the core material. When the content exceeds 5.0% by mass, Granulation may occur.

  The toner mass ratio relative to the carrier is usually 0.01 to 0.1.

  The developer set can be applied to a known image forming apparatus capable of forming an image using clear toner and colored toner, but the colored toner image and the clear toner image are transferred onto the intermediate transfer member. It is preferable to apply it to an image forming apparatus that transfers the image onto a recording medium after overlapping.

  Examples of the present invention will be described below, but the present invention is not limited to the examples. In addition, a part means a mass part.

(Synthesis of crystalline polyester)
In a 5 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, 2500 parts of 1,12-decanediol, 2330 parts of 1,8-octanedioic acid and 4.9 parts of hydroquinone were placed. Then, it was made to react at 180 degreeC for 20 hours. Next, after heating up to 200 degreeC and making it react for 6 hours, it was made to react at 8.3 kPa for 10 hours, and crystalline polyester was obtained. The crystalline polyester resin has a number average molecular weight of 4400, a weight average molecular weight of 15000, a melting point of 70 ° C., an acid value of 25 mgKOH / g, a hydroxyl value of 2.5 mgKOH / g, and a molecular weight of 500 or less. The ratio of the molecular weight of 1000 or less was 3.6%.

(Synthesis of wax dispersant)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene and 300 parts of low molecular weight polyethylene sun wax LEL-400 (manufactured by Sanyo Chemical Industries) having a softening point of 128 ° C. were added, and the temperature was raised to 175 ° C. And replaced with nitrogen. Next, a mixture of 2310 parts of styrene, 270 parts of acrylonitrile, 150 parts of butyl acrylate, 78 parts of di-t-butylperoxyhexahydroterephthalate and 455 parts of xylene was added dropwise over 3 hours, and then at 175 ° C. for 30 minutes. Retained. Further, the solvent was removed to obtain a wax dispersant.

(Synthesis of non-crystalline polyester)
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 229 parts of an ethylene oxide 2-mole adduct of bisphenol A, 529 parts of a propylene oxide 3-mole adduct of bisphenol A, and isophthalic acid 100 Part, 108 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 10 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 30 parts of trimellitic anhydride was added and reacted at 180 ° C. for 3 hours to obtain an amorphous polyester. The amorphous polyester had a number average molecular weight of 1,800, a weight average molecular weight of 5,500, a glass transition point of 50 ° C., and an acid value of 20 mgKOH / g.

(Synthesis of polyester prepolymer)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and the polyester which has a hydroxyl group was obtained. The polyester having a hydroxyl group had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition point of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

  Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts of polyester having a hydroxyl group, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate were allowed to react at 100 ° C. for 5 hours to obtain a polyester prepolymer. Obtained. The polyester prepolymer had a free isocyanate content of 1.53% by mass.

(Synthesis of ketimine)
Into a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were added and reacted at 50 ° C. for 5 hours to obtain ketimine. Ketimine had an amine value of 418 mg KOH / g.

Example 1
<Manufacture of clear two-component developer>
-Preparation of wax dispersion-
In a container equipped with a stir bar and a thermometer, 528 parts of amorphous polyester, 110 parts of hydrocarbon wax Hi-mic-1090 (manufactured by Nippon Seiki Co., Ltd.), 77 parts of a wax dispersant, a metal salicylic acid complex as a charge control agent After adding 22 parts of E-84 (Orient Chemical Industries) and 947 parts of ethyl acetate, it heated up to 80 degreeC and hold | maintained for 5 hours. Next, after cooling to 30 ° C. in 1 hour, 500 parts of ethyl acetate was added and mixed for 1 hour to obtain a mixed solution.

  After transferring 1324 parts of the mixed solution to a container, using a bead mill Ultra Visco Mill (manufactured by IMEX), the liquid feeding speed was 1 kg / h, the peripheral speed of the disk was 6 m / s, and the particle size was 0.5 mm. 80% by volume of zirconia beads were filled and dispersed under conditions of 3 passes. Next, 1042.3 parts of a 65 mass% ethyl acetate solution of amorphous polyester was added, and one pass was performed under the above conditions to obtain a wax dispersion. The wax dispersion had a solid content concentration of 50% by mass.

-Preparation of crystalline polyester dispersion-
After putting 100 g of crystalline polyester and 400 g of ethyl acetate into a 2 L metal container, the temperature was raised to 75 ° C. and quenched in an ice-water bath at a rate of 27 ° C./min. Next, after adding 500 mL of glass beads having a particle diameter of 3 mm, the mixture was dispersed for 10 hours using a batch type sand mill apparatus (manufactured by Campehapio) to obtain a crystalline polyester dispersion.

-Preparation of vinyl resin particle dispersion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) of sulfuric acid ester of ethylene oxide adduct of methacrylic acid, 138 parts of styrene, 138 methacrylic acid And 1 part of ammonium persulfate were added, followed by stirring at 400 rpm for 15 minutes. Next, after heating up to 75 degreeC and making it react for 5 hours, 30 parts of 1 mass% ammonium persulfate aqueous solution was added and it was made to age | cure | ripen at 75 degreeC for 5 hours, and the vinyl-type resin particle dispersion liquid was obtained.

-Preparation of aqueous phase-
990 parts of water, 83 parts of vinyl resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed, and the aqueous phase was mixed. Obtained.

-Preparation of oil phase-
Into a container, 664 parts of a wax dispersion, 109.4 parts of a polyester prepolymer, 73.9 parts of a crystalline polyester dispersion and 4.6 parts of ketimine are used, and then a TK homomixer (manufactured by Koki Kogyo Co., Ltd.) is used. And mixing at 5000 rpm for 1 minute to obtain an oil phase.

-Emulsification-
After putting 850 parts of the oil phase and 1200 parts of the water phase into the container, the mixture was mixed at 13000 rpm for 18 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

-Solvent removal-
In a vessel equipped with a stirrer and a thermometer, 2050 parts of the emulsified slurry and 410 parts of ion-exchanged water were added, and then the solvent was removed at 30 ° C. for 8 hours. Next, the slurry was aged at 45 ° C. for 4 hours to obtain a dispersed slurry.

-Washing-
100 parts of the dispersion slurry was filtered under reduced pressure to obtain a filter cake. Next, 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), followed by filtration to obtain a filter cake. Furthermore, 100 parts of a 10% by mass sodium hydroxide aqueous solution was added to the filter cake, and after mixing for 30 minutes at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), filtration under reduced pressure was performed to obtain a filter cake. Next, 100 parts of 10 mass% hydrochloric acid was added to the filter cake, and after mixing for 10 minutes at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), filtration was performed to obtain a filter cake. Furthermore, 300 parts of ion-exchanged water was added to the filter cake, and after mixing for 10 minutes at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the filtration operation was performed twice to obtain a filter cake.

-Drying and classification-
Next, the filter cake was dried for 48 hours at 45 ° C. using a circulating dryer, and then sieved with a 75 μm mesh to obtain base particles for clear toner.

-Preparation of clear toner-
Using a Henschel mixer, 100 parts of base particles for clear toner, 0.7 parts of hydrophobic silica particles HDK H2000 (manufactured by Clariant Japan) having an average primary particle size of 10 nm, titanium oxide particles MT- having an average primary particle size of 15 nm A clear toner was obtained by mixing 0.3 part of 150A (Taika). The clear toner had a volume average particle size of 4.9 μm.

-Preparation of clear two-component developer-
5 parts of clear toner and 95 parts of a copper-zinc ferrite carrier having a volume-based median diameter of 40 μm and coated with a silicone resin were mixed to obtain a clear two-component developer.

<Manufacture of black two-component developer>
-Preparation of master batch-
Using a Henschel mixer (made by Mitsui Mining Co., Ltd.), 1200 parts of water, 540 parts of carbon black Printex 35 (made by Dexa) having a DBP oil absorption of 42 mL / 100 mg and a pH of 9.5, and 1200 parts of non-crystalline polyester were mixed. A mixture was obtained. Next, the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized using a pulverizer (manufactured by Hosokawa Micron) to obtain a master batch.

-Preparation of pigment / wax dispersion-
In a container equipped with a stir bar and a thermometer, 378 parts of amorphous polyester, 110 parts of a hydrocarbon wax Hi-mic-1090 (manufactured by Nippon Seiki Co., Ltd.), 77 parts of a wax dispersant, a salicylic acid metal complex as a charge control agent After adding 22 parts of E-84 (Orient Chemical Industries) and 947 parts of ethyl acetate, it heated up at 80 degreeC and hold | maintained for 5 hours. Next, after cooling to 30 ° C. in 1 hour, 500 parts of a master batch and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a mixed solution.

  After transferring 1324 parts of the mixed solution to a container, using a bead mill Ultra Visco Mill (manufactured by IMEX), the liquid feeding speed was 1 kg / h, the peripheral speed of the disk was 6 m / s, and the particle size was 0.5 mm. 80% by volume of zirconia beads were filled and dispersed under conditions of 3 passes. Next, after adding 1042.3 parts of a 65% by weight ethyl acetate solution of amorphous polyester, one pass was performed under the above conditions to obtain a pigment / wax dispersion. The pigment / wax dispersion had a solid content of 50% by mass.

-Preparation of aqueous phase-
An aqueous phase was obtained in the same manner as in <Production of clear two-component developer>.

-Preparation of oil phase-
An oil phase was obtained in the same manner as in <Production of clear two-component developer> except that a pigment / wax dispersion was used instead of the wax dispersion.

-Emulsification-
After putting 850 parts of an oil phase and 1200 parts of an aqueous phase into a container, the mixture was mixed for 20 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

-Solvent removal, washing, drying and classification-
Base particles for black toner were obtained in the same manner as in <Production of clear two-component developer> except that the obtained emulsified slurry was used.

-Preparation of black toner-
Using a Henschel mixer, 100 parts of black toner base particles, hydrophobic silica particles HDK H2000 (manufactured by Clariant Japan) with an average primary particle size of 10 nm, 0.8 parts of titanium oxide particles MT- with an average primary particle size of 15 nm A black toner was obtained by mixing 0.4 part of 150A (Taika). The black toner had a volume average particle size of 4.2 μm.

-Preparation of black two-component developer-
A black two-component developer was obtained in the same manner as in <Preparation of Clear Two-Component Developer> except that a black toner was used instead of the clear toner.

(Example 2)
<Manufacture of clear two-component developer>
A clear two-component developer was obtained in the same manner as in Example 1 except that the amount of hydrophobic silica particles having an average primary particle size of 10 nm was changed to 0.3 part in the preparation of the clear toner. The clear toner had a volume average particle size of 4.9 μm.

<Manufacture of black two-component developer>
-Emulsification-A black two-component developer was obtained in the same manner as in Example 1 except that the mixture was mixed at 13000 rpm for 19 minutes. The black toner had a volume average particle size of 4.7 μm.

Example 3
<Manufacture of clear two-component developer>
In the emulsification, the mixture was mixed at 13000 rpm for 11 minutes, and in the preparation of the clear toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A clear two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The clear toner had a volume average particle size of 8.4 μm.

<Manufacture of black two-component developer>
In the emulsification, mixing is performed at 13000 rpm for 14 minutes, and in the preparation of the black toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm is set to 0. A black two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The black toner had a volume average particle diameter of 7.2 μm.

Example 4
<Manufacture of clear two-component developer>
In the emulsification, the mixture was mixed at 13000 rpm for 11 minutes, and in the preparation of the clear toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A clear two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The clear toner had a volume average particle size of 8.4 μm.

<Manufacture of black two-component developer>
In the emulsification, the mixture was mixed at 13000 rpm for 12 minutes, and in the preparation of the black toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A black two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The black toner had a volume average particle size of 8.2 μm.

(Example 5)
<Manufacture of clear two-component developer>
In the emulsification, mixing was performed at 13,000 rpm for 17 minutes, and in the preparation of the clear toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A clear two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The clear toner had a volume average particle size of 5.5 μm.

<Manufacture of black two-component developer>
-Emulsification-A black two-component developer was obtained in the same manner as in Example 1 except that mixing was performed at 13000 rpm for 18 minutes. The black toner had a volume average particle size of 4.8 μm.

(Comparative Example 1)
<Manufacture of clear two-component developer>
A clear two-component developer was obtained in the same manner as in Example 1 except that the amount of hydrophobic silica particles having an average primary particle size of 10 nm was changed to 0.3 part in the preparation of the clear toner. . The clear toner had a volume average particle size of 4.9 μm.

<Manufacture of black two-component developer>
-Emulsification-A black two-component developer was obtained in the same manner as in Example 1 except that mixing was performed at 13000 rpm for 18 minutes. The black toner had a volume average particle size of 4.9 μm.

(Comparative Example 2)
<Manufacture of clear two-component developer>
In the emulsification, mixing was performed at 13000 rpm for 16 minutes, and in the preparation of the clear toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A clear two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The clear toner had a volume average particle size of 6.0 μm.

<Manufacture of black two-component developer>
-Emulsification-A black two-component developer was obtained in the same manner as in Example 1 except that mixing was performed at 13000 rpm for 18 minutes. The black toner had a volume average particle size of 4.9 μm.

(Comparative Example 3)
<Manufacture of clear two-component developer>
-Emulsification-Mixing at 13000 rpm for 19 minutes,-Preparation of clear toner-Same as Example 1 except that the amount of hydrophobic silica particles having an average primary particle size of 10 nm was changed to 0.3 parts Thus, a clear two-component developer was obtained. The clear toner had a volume average particle size of 4.5 μm.

<Manufacture of black two-component developer>
In the same manner as in Example 1, a black two-component developer was obtained. The black toner had a volume average particle size of 4.2 μm.

(Comparative Example 4)
<Manufacture of clear two-component developer>
In the emulsification, the mixture was mixed at 13000 rpm for 11 minutes, and in the preparation of the clear toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm was set to 0. A clear two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 1 part. The clear toner had a volume average particle size of 8.5 μm.

<Manufacture of black two-component developer>
In the emulsification, mixing is performed at 13000 rpm for 13 minutes, and in the preparation of the black toner, the addition amount of the hydrophobic silica particles having an average primary particle size of 10 nm and the titanium oxide particles having an average primary particle size of 15 nm is set to 0. A black two-component developer was obtained in the same manner as in Example 1 except that the amount was changed to 2 parts. The black toner had a volume average particle size of 7.3 μm.

  Table 1 shows the characteristics of the clear toner and the black toner in Examples and Comparative Examples.

(Volume average particle size)
The volume average particle diameter of the toner is measured using a particle size measuring device Multisizer III (manufactured by Beckman Coulter) with an aperture diameter of 100 μm, and using analysis software Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.). And analyzed. Specifically, after adding 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate) solution Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 g of toner in a 100 mL glass beaker. Stir in a micropartel. Next, after adding 80 mL of ion-exchange water, it was dispersed for 10 minutes using an ultrasonic disperser W-113MK-II (manufactured by Honda Electronics Co., Ltd.) to obtain a dispersion. Further, Isoton III (manufactured by Beckman Coulter) was used as a measurement solution, and the dispersion was dropped so that the concentration indicated by the particle size measuring device was 8 ± 2%, and the volume average particle size was measured.

  Next, the two-component developer sets of Examples and Comparative Examples were evaluated.

(Low temperature fixability)
As a fixing roller, type 6200 paper (Ricoh Co., Ltd.) using a device that has modified the fixing unit of a copying machine MF2200 (manufactured by Ricoh) and a clear two-component developer (or black two-component developer) using a Teflon (registered trademark) roller. Made a copy test. Specifically, the fixing lower limit temperature was determined by changing the fixing temperature. The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 to 150 mm / s, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.

(Chargeability)
In a 23 ° C. and 55% RH environment, a clear two-component developer (or black two-component developer) is allowed to stand for 30 minutes to adjust the humidity, and then a stainless steel cylinder having a diameter of 30 mm and a width of 30 mm. A clear two-component developer (or black two-component developer) was placed in the pot and stirred at 600 rpm for 10 minutes. Next, the charge amount of the clear two-component developer (or black two-component developer) was measured using a blow-off device TB-200 (manufactured by Toshiba Chemical Corporation). Specifically, 1 g of the two-component developer was put into a measurement gauge having a mesh opening of 635 mesh, and then blown off for 30 seconds. The charge amount of the clear two-component developer (or black two-component developer) is obtained by measuring the charge amount Q [μC] and mass M [g] of the scattered powder, and the formula Q / M
I asked for it.

(Heat resistant storage stability)
After the clear toner (or black toner) was stored at 50 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was determined. The heat-resistant storage stability is ◎ when the residual ratio is less than 10%, ◯ when it is 10% or more and less than 20%, Δ when it is 20% or more and less than 30%, and when it is 30% or more. Judged as x.

(Granularity of solid image)
A monochrome image obtained by dividing the gradation values 0 to 255 into 36 levels and arranging solid images filled with the respective gradation values is input as an evaluation chart (see FIG. 1). Under image conditions and (2) halftone processing, the granularity of the output solid image was measured using Imagio MP C3000 (manufactured by Ricoh), clear two-component developer and black two-component developer. Specifically, the granularity was calculated by converting a solid image read by a scanner into a spatial frequency component, and performing correction by visual spatial frequency characteristics (VTF) and correction by average brightness of the image. In addition, when the granularity is less than 0.15, ◎, when 0.15 or more and less than 0.30, ◯, when 0.30 or more and less than 0.40, Δ, or 0.40 or more Was determined as x.
(1) A black solid image was output using black toner, and then a clear solid image was output on the black solid image using clear toner. At this time, the developing bias and the charging bias are adjusted so that the black solid image adhesion amount is 0.6 mg / cm ² when the laser power and lighting time of the laser light source of the exposure unit of the black image forming unit is 100%. did. Further, the developing bias and the charging bias were adjusted so that the amount of adhesion of the clear solid image when the laser power and lighting time of the laser light source of the exposure unit of the clear image forming unit was 100% was 0.3 mg / cm ² . .
(2) Halftone processing A, which is a ternary 190L72D line dither using a threshold matrix (see FIG. 2), was used (see Japanese Patent Application Laid-Open No. 2009-222301).

  2A is a threshold matrix of output gradation values 128, and FIG. 2B is a threshold matrix of output gradation values 256.

  Table 2 shows the evaluation results of the two-component developer sets of Examples and Comparative Examples.

From Table 2, it can be seen that the two-component developer sets of Examples 1 to 5 are excellent in low-temperature fixability and heat-resistant storage stability and can form solid images with excellent granularity.

  On the other hand, since the two-component developer set of Comparative Example 1 has an A / B of 1.0 or less, the low-temperature fixability and heat-resistant storage stability of the clear toner cannot be compatible.

  In the two-component developer set of Comparative Example 2, since A / B exceeds 1.2, the granularity of the solid image is lowered.

  In the two-component developer set of Comparative Example 3, since A is less than 4.8, the low-temperature fixability and heat-resistant storage stability of the clear toner cannot be compatible, and the solid image granularity is lowered.

  In the two-component developer set of Comparative Example 4, since A exceeds 8.4, the granularity of the solid image is lowered.

JP 2002-236396 A

Claims (8)

Having clear toner and colored toner,
The clear toner includes a binder resin and a release agent,
The colored toner includes a binder resin, a pigment, and a release agent,
When the volume average particle diameter of the clear toner is A [μm] and the volume average particle diameter of the colored toner is B [μm], the formula 4.8 ≦ A ≦ 8.4
1.0 <A / B ≦ 1.2
A toner set characterized by satisfying The clear toner includes crystalline polyester,
The toner set according to claim 1, wherein the colored toner includes crystalline polyester. The clear toner has a content of the crystalline polyester of 5% by mass or more and 20% by mass or less.
The toner set according to claim 2, wherein a content of the crystalline polyester in the clear toner is equal to or more than a content of the crystalline polyester in the colored toner.   The toner set according to claim 1, wherein the release agent is a hydrocarbon wax or an ester wax.   The toner set according to claim 1, wherein a release agent contained in the colored toner is the same as a release agent contained in the clear toner. The binder resin includes a polyester having a crosslinked structure and an amorphous polyester having no crosslinked structure,
The polyester having the crosslinked structure is synthesized by reacting a polyester prepolymer having a group capable of reacting with an active hydrogen group and a compound having an active hydrogen group. The toner set according to claim 5.   A developer set comprising the toner set according to claim 1.   An image forming apparatus that forms an image using the developer set according to claim 7.