JP5428627B2 - Toner set, developer set, and image forming apparatus - Google Patents

Description

The present invention relates to a toner set , a developer set, and an image forming apparatus .

  In recent years, print-on-demand (POD) that does not require a plate-making process has grown. POD using an electrophotographic method is good at printing a small number of copies and variable printing, and is expected as an alternative to light printing. For this reason, a full color image formed using an electrophotographic image forming apparatus is required to be glossy.

  In Patent Document 1, a color toner image containing a thermoplastic resin and a colorant is used to form a color toner image on the surface of a recording medium by electrophotography, and then a transparent toner is transferred onto or around the color toner image. A fixing method is disclosed. Further, it contains 90 mol% or more of an aromatic component as an acid-derived constituent component with respect to the total acid-derived constituent component, and a linear aliphatic diol and bisphenol S or bisphenol S alkylene oxide adduct as an alcohol-derived constituent component are all alcohols. A transparent toner containing 70% by mass or more of the total binder resin component is disclosed as a binder resin including a polyester resin in the range of 85 to 98 mol% and 2 to 15 mol%, respectively, with respect to the derived constituent component. . At this time, when a film having a thickness of 20 μm is obtained from the polyester resin, the luminous reflectance Y of the film is 1.5% or less.

  However, these transparent toners have insufficient affinity with color toners containing resins having urethane bonds and / or urea bonds as binder resins, and therefore when used with such color toners, the degree of haze is low. There is a problem that the color reproducibility is lowered and the color reproducibility is changed.

  At this time, since the resin having a urethane bond and / or urea bond has a small decrease in elastic modulus due to heating, when the color toner containing the resin having a urethane bond and / or urea bond is heat-fixed, the particles between the color toners The world is likely to remain. For this reason, when a transparent toner is used together with a color toner containing a resin having a urethane bond and / or a urea bond, it is considered that the haze degree decreases due to the influence of the grain boundary between the color toners.

The present invention forms an image by using a preparative toner set and the developer sets and developer set that can be in view of the problems above-mentioned prior art has, to suppress the degradation and color reproducibility of the change of f noise level and to provide an image forming apparatus you.

Invention of claim 1, a toner set including a color toner, the transparent toner, the color toner, a resin having a urethane bond and / or urea bond, seen containing a colorant, wherein the transparent toner includes a polyol resin, free of colorant, the polyol resin, react with at least an epoxy resin, a dihydric phenol, a resin obtained by condensing a divalent alkylene oxide adduct and polyhydric carboxylic acid phenol It is characterized by being obtained.

According to a second aspect of the present invention, in the toner set according to the first aspect , the epoxy resin has a general formula.

（式中、Ｒ^１は、炭素数が１以上４以下のアルキレン基又は炭素数が１以上４以下のヒドロキシル基を有するアルキレン基であり、ｋ及びｎは、それぞれ独立に、０又は１であり、ｌは、１以上１０以下の整数であり、ｍは、０以上１２０以下の整数である。ただし、ｍ及びｎが０である場合を除く。）
で表される化合物であることを特徴とする。

(In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms, and k and n are each independently 0 or 1; , L is an integer from 1 to 10, and m is an integer from 0 to 120, except when m and n are 0.)
It is a compound represented by these.

According to a third aspect of the present invention, in the toner set according to the first or second aspect, the dihydric phenol is bisphenol A.

According to a fourth aspect of the present invention, in the toner set according to any one of the first to third aspects, the resin obtained by condensing the alkylene oxide adduct of the dihydric phenol and the polyvalent carboxylic acid is generally formula

（式中、Ｒ^２は、炭素数が１以上４以下のアルキレン基又は炭素数が１以上４以下のヒドロキシル基を有するアルキレン基であり、ｏ及びｐは、それぞれ独立に、０以上２００以下の整数である。ただし、ｏ及びｐが０である場合を除く。）
で表される化合物であることを特徴とする。

(In the formula, R ² is an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms, and o and p are each independently 0 or more and 200 or less. Integer, except when o and p are 0.
It is a compound represented by these.

According to a fifth aspect of the present invention, in the toner set according to any one of the first to fourth aspects, the polyol resin has a hydroxyl value of 25 KOHmg / g or more and 60 KOHmg / g or less.

The invention described in claim 6 is the toner set according to any one of claims 1 to 7, wherein the polyol resin has an epoxy equivalent of 2 × 10 ⁴ g / eq or more.

According to a seventh aspect of the present invention, in the toner set according to any one of the first to eighth aspects, the resin having a urethane bond and / or a urea bond is a urea-modified polyester.

According to an eighth aspect of the present invention, in the toner set according to any one of the first to seventh aspects, the color toner is manufactured using a dissolution suspension method or a polyester elongation method. To do.

The invention according to claim 9 is a developer set comprising a developer containing a color toner and a developer containing a transparent toner, wherein the color toner comprises a resin having a urethane bond and / or a urea bond, The transparent toner contains a polyol resin, does not contain a colorant, and the polyol resin condenses at least an epoxy resin, a dihydric phenol, an alkylene oxide adduct of a dihydric phenol, and a polycarboxylic acid. It is obtained by reacting with a resin obtained in this manner.

The invention of claim 10 is the image forming apparatus, and forming an image using the developer set forth in 請 Motomeko 9.

According to the present invention, there is provided an image forming apparatus that to form an image using the preparative toner set and the developer sets and developer set capable of suppressing the deterioration and color reproducibility of the change of f noise level be able to.

It is a figure which shows an example of the image forming apparatus used by this invention.

  Next, the form for implementing this invention is demonstrated with drawing.

  The transparent toner of the present invention is used together with a color toner containing a resin having a urethane bond and / or a urea bond, and at least an epoxy resin (a), a dihydric phenol (b), and an alkylene oxide adduct of a dihydric phenol ( A polyol resin obtained by reacting c1) and a resin (c) obtained by condensing polycarboxylic acid (c2) is included. For this reason, the fall of a haze degree and color reproducibility can suppress a fluctuation | variation.

  Although it does not specifically limit as an epoxy resin (a), Dihydric phenols, such as bisphenol A, bisphenol F, bisphenol S, or the alkylene oxide addition product of a bihydric phenol, epichlorohydrin, (beta) -methyl epichlorohydrin, etc. And may be used in combination of two or more. Although it does not specifically limit as alkylene oxide, Ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned, You may substitute by the hydroxyl group.

  The epoxy resin (a) has a general formula from the viewpoint of affinity with the color toner and abrasion resistance.

（式中、Ｒ^１は、炭素数が１〜４のアルキレン基又は炭素数が１〜４のヒドロキシル基を有するアルキレン基であり、ｋ及びｎは、それぞれ独立に、０又は１であり、ｌは、１〜１０の整数であり、ｍは、０〜１２０の整数である。ただし、ｍ及びｎが０である場合を除く。）
で表される化合物であることが好ましい。

(In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms or an alkylene group having a hydroxyl group having 1 to 4 carbon atoms, k and n are each independently 0 or 1, Is an integer from 1 to 10, and m is an integer from 0 to 120, except when m and n are 0.)
It is preferable that it is a compound represented by these.

  The epoxy resin (a) may be used in combination with a first epoxy resin having a number average molecular weight of 360 to 2000 and a second epoxy resin having a number average molecular weight of 3000 to 10,000 from the viewpoint of fixability and gloss. preferable. At this time, the mass ratio of the first epoxy resin to the second epoxy resin is preferably 0.25 to 1, and more preferably 3/7 to 2/3. When this mass ratio exceeds 1, or when the number average molecular weight of the first epoxy resin is less than 360, the gloss may be excessively increased or the storage stability may be deteriorated. On the other hand, when the mass ratio is less than 0.25 or when the number average molecular weight of the second epoxy resin exceeds 10,000, gloss may be insufficient or fixability may be deteriorated.

  In the present invention, the number average molecular weight and the weight average molecular weight can be measured using gel permeation chromatography (GPC).

  Although it does not specifically limit as bivalent phenol (b), Bisphenol A, bisphenol F, bisphenol S etc. are mentioned, You may use 2 or more types together. Among these, bisphenol A is preferable from the viewpoint of affinity with the color toner and abrasion resistance.

  The dihydric phenol alkylene oxide adduct (c1) in the resin (c) is not particularly limited, and examples thereof include dihydric phenol alkylene oxide adducts such as bisphenol A, bisphenol F, and bisphenol S. May be. Although it does not specifically limit as alkylene oxide, Ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned, You may substitute by the hydroxyl group.

  The polyvalent carboxylic acid (c2) in the resin (c) is not particularly limited, but maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, Divalent carboxylic acids such as octyl succinic acid, dodecyl succinic acid, cyclohexanedicarboxylic acid, methylmedicic acid, phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid; trimellitic acid, pyromellitic acid, 1,2 , 4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, etc. And trivalent or tetravalent carboxylic acid, and the like may be used in combination of two or more.In place of the polyvalent carboxylic acid (c2), an anhydride of the polyvalent carboxylic acid (c2); a derivative such as a lower alkyl ester such as methyl ester or butyl ester may be used.

  The resin (c) has a general formula from the viewpoint of affinity with the color toner and abrasion resistance.

（式中、Ｒ^２は、炭素数が１〜４のアルキレン基又は炭素数が１〜４のヒドロキシル基を有するアルキレン基であり、ｏ及びｐは、それぞれ独立に、０〜２００の整数である。）
で表される化合物であることが好ましい。

(In the formula, R ² represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having a hydroxyl group having 1 to 4 carbon atoms, and o and p are each independently an integer of 0 to 200. .)
It is preferable that it is a compound represented by these.

  The resin (c) preferably has a number average molecular weight of 600 to 1600, more preferably 800 to 1300. If the number average molecular weight is less than 600, the gloss may be excessively increased or the storage stability may be deteriorated. On the other hand, when the number average molecular weight exceeds 1600, gloss may be insufficient or fixability may be deteriorated.

  When synthesizing the polyol resin, it is preferable to react 25 to 70% by mass of the epoxy resin (a), 10 to 40% by mass of the dihydric phenol (b) and 5 to 20% by mass of the resin (c).

  The hydroxyl value of the polyol resin is preferably 25-60 KOHmg / g, more preferably 35-55 KOHmg / g. When the hydroxyl value is less than 25 KOHmg / g, when used together with a color toner containing a resin having a urethane bond and / or a urea bond, the haze degree may decrease or the color reproducibility may fluctuate. If it exceeds 60 KOHmg / g, the environmental stability of the chargeability of the transparent toner may be lowered.

  In the present invention, the hydroxyl value can be measured according to JIS K 0070.

  Moreover, since the polyol resin has a structural unit derived from the resin (c), the transparent toner of the present invention is excellent in gloss.

The polyol resin preferably has an epoxy equivalent of 2 × 10 ⁴ g / eq or more from the viewpoint of production stability of the transparent toner. The epoxy equivalent can be measured according to the indicator titration method of 4.2 of JIS K 7236. However, epoxy equivalent detection limit is about 2 × ¹⁰ 4 g / eq, if 2 × ¹⁰ 4 g / eq or more epoxy groups is substantially absent.

  For this reason, when synthesizing a polyol resin, an epoxy group may be capped. The compound for capping the epoxy group is not particularly limited, but phenol derivatives such as phenol, cresol, isopropylphenol, amylphenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol; aromatic carboxylic acids such as benzoic acid, Examples thereof include carboxylic acids such as aliphatic carboxylic acids such as stearic acid. When capping the epoxy group, the reaction can be carried out in a solvent such as xylene in the presence of a catalyst such as a lithium chloride catalyst.

  The softening point of the polyol resin is preferably 90 to 160 ° C, and more preferably 100 to 130 ° C. When the softening point is less than 90 ° C., the heat-resistant storage stability of the transparent toner is lowered, and the members and carriers in the developing device may be easily contaminated. May decrease.

  In the present invention, the softening point can be measured using a flow tester CFT-500D (manufactured by Shimadzu Corporation).

  The glass transition point of the polyol resin is preferably 50 to 75 ° C, more preferably 55 to 70 ° C. When the glass transition point is less than 50 ° C., the heat-resistant storage stability of the transparent toner is reduced, and agglomerates are likely to be generated in the toner bottle or the developing device. In some cases, the fixability may decrease.

  In the present invention, the glass transition point can be measured using a differential scanning calorimeter DSC-60A (manufactured by Shimadzu Corporation).

  The transparent toner of the present invention may further contain a binder resin other than the polyol resin. The binder resin other than the polyol resin is not particularly limited, and examples thereof include vinyl resins such as polyester and styrene-acrylic resins, epoxy resins, polycarbonate, polyurethane, and resins having two or more units including a polyester unit. Two or more kinds may be used in combination.

  The transparent toner of the present invention may further contain a release agent, a charge control agent, a fluidity improver, a cleaning property improver and the like.

  The release agent is not particularly limited, but a carbonyl group-containing wax such as polyalkanoic acid ester, polyalkanol ester, polyalkanoic acid amide, polyalkylamide, and dialkyl ketone; polyolefin wax such as polyethylene wax and polypropylene wax; paraffin wax Long chain hydrocarbons such as sazol wax and the like may be used in combination. Among these, carbonyl group-containing waxes are preferable, and polyalkanoic acid esters are particularly preferable.

  Examples of polyalkanoic acid esters include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distea. Rate and the like.

  Examples of polyalkanol esters include tristearyl trimellitic acid and distearyl maleate.

  Examples of the polyalkanoic acid amide include dibehenyl amide.

  Examples of the polyalkylamide include trimellitic acid tristearylamide.

  Examples of dialkyl ketones include distearyl ketone.

  The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 160 ° C., cold offset may easily occur during low-temperature fixing.

  In the present invention, the melting point can be measured using a differential scanning calorimeter DSC-60A (manufactured by Shimadzu Corporation).

  The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the release agent. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.

  The content of the release agent in the transparent toner of the present invention is preferably 0 to 40% by mass, more preferably 3 to 20% by mass, and particularly preferably 3 to 10% by mass. If the content of the release agent exceeds 40% by mass, the haze degree of the transparent toner may decrease, the fluidity of the transparent toner may decrease, or filming may occur on the carrier or the photoreceptor. is there.

  The charge control agent is not particularly limited, but triphenylmethane dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus Examples include simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like.

  The content of the charge control agent in the transparent toner of the present invention is preferably 0.1 to 10% by mass and more preferably 0.2 to 5% by mass with respect to the binder resin. When the content of the charge control agent is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the transparent toner increases and the developer fluidity is increased. May decrease or the image density may decrease.

  Although it does not specifically limit as a fluid improvement agent, A silica, titania, an alumina, a tin oxide, an antimony oxide etc. are mentioned, You may use 2 or more types together. Of these, hydrophobized silica, hydrophobized titania, hydrophobized titanium oxide, and hydrophobized alumina are preferable.

  The surface treatment agent for hydrophobizing the fluidity improver is not particularly limited, but silane coupling agents such as dialkyldihalosilane, trialkylhalosilane, alkyltrihalosilane, hexaalkyldisilazane; silylating agent, fluorination Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and silicone varnishes.

  The average primary particle size of the fluidity improver is preferably 3 to 150 nm, and more preferably 8 to 70 nm. When the average primary particle size is less than 3 nm, the fluidity improver may be buried in the transparent toner, and when it exceeds 150 nm, the fluidity improver may be easily detached from the transparent toner.

  The content of the fluidity improver in the transparent toner of the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass.

  The cleaning improver is not particularly limited, and examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate; resin particles such as polymethyl methacrylate, polystyrene, silicone, benzoguanamine, and nylon.

  The resin particles preferably have a weight average particle diameter of 0.01 to 1 μm.

  The content of the cleaning property improving agent in the transparent toner of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass.

  The method for producing the transparent toner of the present invention is not particularly limited, and examples thereof include a pulverization method, a polymerization method, an emulsion aggregation method, a dissolution suspension method, and a spray granulation method.

  As an example, a method for producing a transparent toner using a pulverization method will be described below. The pulverization method is a method for producing base particles by pulverizing and classifying a kneaded product obtained by melting and kneading a toner material containing a binder resin, a release agent, a charge control agent and the like.

  Specifically, first, a mixture obtained by mixing toner materials is charged into a melt kneader and melt kneaded. The melt kneader is not particularly limited, but is a KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.), a twin screw extruder (manufactured by Casey Kay Corp.), PCM type Examples thereof include a screw extruder (manufactured by Ikekai Iron Works Co., Ltd.) and a kneader (manufactured by Busus).

  Next, the melt-kneaded kneaded product is pulverized. When the kneaded product is pulverized, it is preferable that the kneaded product is coarsely pulverized and then finely pulverized. The method of pulverizing the kneaded product is not particularly limited, but the method of pulverizing the kneaded product by colliding with the impingement plate in the jet stream, the method of pulverizing the kneaded product by colliding with each other in the jet stream, mechanical rotation And a method of pulverizing the kneaded material in a narrow gap between the rotor and the stator.

  Furthermore, the pulverized kneaded product is classified. When classifying the pulverized kneaded product, first, fine powder is removed using a cyclone, a decanter, a centrifuge, or the like. Next, the coarse powder is removed from the kneaded product from which the fine powder has been removed by using centrifugal force or the like in an air current to obtain base particles.

  Next, after adding additives, such as a fluid improvement agent and a cleaning property improvement agent, to a base particle, it mixes and stirs using a mixer. Thereby, the surface of the base particle is coated while the additive is crushed, and a transparent toner is obtained.

  The transparent toner of the present invention may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer. However, when applied to an ultrahigh-speed printing system that can handle POD, etc. From the viewpoint of improving the service life, a two-component developer is preferable.

  The carrier preferably has a core material and a coating layer that covers the core material.

  Although it does not specifically limit as a material which comprises a core material, 50-90 emu / g manganese-strontium type material, manganese-magnesium type material, etc. are mentioned, You may use 2 or more types together. At this time, since high image density can be ensured, a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g is preferable. Further, a weakly magnetized material such as a copper-zinc-based material of 30 to 80 emu / g is preferable because it can weaken the contact with the electrostatic latent image carrier and is advantageous for high image quality.

  The weight average particle diameter (D50) of the core material is preferably 10 to 200 μm, and more preferably 40 to 100 μm. If the weight average particle diameter (D50) is less than 10 μm, the magnetization per particle may be small and carrier scattering may occur. If it exceeds 200 μm, the specific surface area will decrease and toner scattering will occur. There are things to do.

  The material constituting the coating layer is not particularly limited, but an 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, tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Fluoroterpolymers such as terpolymers; silicone resins and the like, and two or more of them may be used in combination. Of these, silicone resins are preferred.

  The silicone resin is not particularly limited, and examples thereof include straight silicone resins; modified silicone resins such as alkyd-modified silicone resins, epoxy-modified silicone resins, acrylic-modified silicone resins, and urethane-modified silicone resins.

  Examples of commercially available straight silicone resins include KR271, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.); SR2400, SR2406, SR2410 (manufactured by Toray Dow Corning Silicone).

  Commercially available modified silicone resins include alkyd-modified silicone resin KR206, acrylic-modified silicone resin KR5208, epoxy-modified silicone resin ES1001N, urethane-modified silicone resin KR305 (manufactured by Shin-Etsu Chemical Co., Ltd.); epoxy-modified silicone resin SR2115, alkyd-modified silicone resin SR2110 (manufactured by Toray Dow Corning Silicone) or the like.

  The silicone resin may be used alone, or may be used together with a component that crosslinks, a component that adjusts the charge amount, and the like.

  The coating layer may further include conductive powder or the like. Although it does not specifically limit as a material which comprises electroconductive powder, A metal, carbon black, a titanium oxide, a tin oxide, a zinc oxide etc. are mentioned.

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

  The coating layer can be formed by dissolving a silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material, drying it, and baking it. Although it does not specifically limit as a coating method, A dipping method, a spray method, a brush coating method, etc. are mentioned.

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

  When baking, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like can be used, or a microwave can be used.

  The content of the coating layer in the carrier is preferably 0.01 to 5.0% by mass. When the content of the coating layer is less than 0.01% by mass, the coating layer may not be uniformly formed on the surface of the core material. When the content exceeds 5.0% by mass, the coating layer becomes too thick. As a result, carriers may be united and a uniform carrier may not be obtained.

  The content of the transparent toner in the two-component developer is preferably 1 to 10% by mass with respect to the carrier.

  Next, a color toner containing a resin having a urethane bond and / or a urea bond used with the transparent toner of the present invention will be described.

  Although it does not specifically limit as resin which has a urethane bond and / or a urea bond, Polyester etc. which have a polyurethane, a polyurea, a urethane bond, and / or a urea bond are mentioned, You may use 2 or more types together. Among these, urea-modified polyester is preferable because it can achieve both low-temperature fixability, hot offset resistance, and heat-resistant storage stability.

  The resin having a urethane bond and / or a urea bond is obtained by reacting a polyester or compound having a functional group capable of reacting with an active hydrogen group and a polyester or compound having an active hydrogen group. Examples of the combination of a functional group capable of reacting with an active hydrogen group and an active hydrogen group include an isocyanate group and a hydroxyl group, and an isocyanate group and an amino group.

  As an example, a method for synthesizing a urea-modified polyester by reacting an isocyanate group-containing polyester (hereinafter referred to as prepolymer (A)) and an amino group-containing compound (B) will be described. At this time, the prepolymer (A) is obtained by reacting a polyester having a hydroxyl group with a polyvalent isocyanate, and the polyester having a hydroxyl group is obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. can get.

  The polyhydric alcohol is preferably a dihydric alcohol or a mixture of a dihydric alcohol and a trihydric or higher alcohol.

  Examples of the divalent alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and the like. Alkylene glycol; alkylene ether glycol such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol; alicyclic diol such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A; bisphenol Bisphenols such as A, bisphenol F and bisphenol S; alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide of alicyclic diols Side adduct, ethylene oxide bisphenols, propylene oxide, alkylene oxide adducts such as butylene oxide. These may be used alone or in combination. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferable, and alkylene oxide adducts of bisphenols or mixtures of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms are preferred. Further preferred.

  Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol; trihydric or higher phenols such as trisphenol PA, phenol novolac, and cresol novolac; An alkylene oxide adduct of phenols having a valence higher than that may be used, and two or more types may be used in combination.

  The polyvalent carboxylic acid is preferably a divalent carboxylic acid or a mixture of a divalent carboxylic acid and a trivalent or higher carboxylic acid.

  Divalent carboxylic acids include alkylene dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; alkenylene dicarboxylic acids such as maleic acid and fumaric acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid An acid etc. are mentioned, You may use 2 or more types together. Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms or aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  Examples of the trivalent or higher carboxylic acid include aromatic carboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid.

  In place of the polyvalent carboxylic acid, an anhydride of the polyvalent carboxylic acid or a lower alkyl ester such as methyl ester, ethyl ester or isopropyl ester may be used.

  In the present invention, the prepolymer (A) may be synthesized using a polyester having an active hydrogen group such as an amino group, a carboxyl group, or a mercapto group instead of the polyester having a hydroxyl group.

  Although it does not specifically limit as polyvalent isocyanate, Aliphatic isocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 6- diisocyanato methyl caproate; Cycloaliphatic isocyanates, such as isophorone diisocyanate, cyclohexylmethane diisocyanate; Examples thereof include aromatic isocyanates such as isocyanate and diphenylmethane diisocyanate; aromatic aliphatic isocyanates such as α, α, α ′, α′-tetramethylxylylene diisocyanate; isocyanurates and the like.

  Instead of the polyvalent isocyanate, a compound obtained by blocking the polyvalent isocyanate with a phenol derivative, oxime, caprolactam or the like may be used.

  The equivalent ratio of the isocyanate group of the polyvalent isocyanate to the hydroxyl group of the polyester having a hydroxyl group and the polyester in the reaction of the polyvalent isocyanate is usually from 1 to 5, preferably from 1.2 to 4, and preferably from 1 to 4 5 to 2.5 is more preferable. If this equivalent ratio exceeds 5, the low-temperature fixability of the color toner may be lowered. If it is less than 1, the urea bond content in the urea-modified polyester becomes small, and the hot offset resistance of the color toner. May decrease.

  The content of isocyanate groups per molecule of the prepolymer (A) is usually 1 or more, preferably 1.5 to 3, more preferably 1.8 to 2.5. If the isocyanate group content is less than 1, the molecular weight of the urea-modified polyester is reduced, and the hot offset resistance of the color toner may be lowered.

  Although it does not specifically limit as a compound (B) which has an amino group, A bivalent amine, a trivalent or more amine, amino alcohol, an amino mercaptan, an amino acid etc. are mentioned, You may use 2 or more types together. Among these, a divalent amine or a mixture of a divalent amine and a trivalent or higher amine is preferable.

  Examples of divalent amines include aromatic diamines such as phenylenediamine, diethyltoluenediamine, and 4,4′-diaminodiphenylmethane; 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, and isophoronediamine. Alicyclic diamine; Aliphatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine and the like.

  Examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine.

  Examples of amino alcohols include ethanolamine and hydroxyethylaniline.

  Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of amino acids include aminopropionic acid and aminocaproic acid.

  Instead of the compound (B) having an amino group, ketimine obtained by blocking the amino group of the compound (B) having an amino group with a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, oxazolidine blocked with an aldehyde, or the like is used. May be.

  When the prepolymer (A) and the compound (B) having an amino group are reacted, the equivalent ratio of the isocyanate group of the prepolymer (A) to the amino group of the compound (B) is usually 0.5 to 2. 2/3 to 1.5 are preferable, and 5/6 to 1.2 are more preferable. When this equivalent ratio is less than 0.5 or exceeds 2, the molecular weight of the urea-modified polyester may become small and low, and the hot offset resistance of the color toner may be lowered.

  In the present invention, the urea-modified polyester may have a urethane bond together with a urea bond. The equivalent ratio of the urethane bond to the urea bond is usually from 0 to 9, preferably from 0.25 to 4, and more preferably from 2/3 to 7/3. If this equivalent ratio exceeds 9, the hot offset resistance of the color toner may be lowered.

  The weight average molecular weight of the urea-modified polyester is usually 5000 to 25000, preferably 8000 to 20000, and more preferably 13,000 to 18000. If the weight average molecular weight is less than 5,000, the heat-resistant storage stability of the color toner may be lowered, and if it exceeds 25,000, the low-temperature fixability of the color toner may be lowered.

  The acid value of the urea-modified polyester is usually 15 to 45 mgKOH / g, and preferably 20 to 35 mgKOH / g. If the acid value is less than 15 mgKOH / g, the low-temperature fixability may be lowered, and if it exceeds 45 mgKOH / g, the negative chargeability of the color toner becomes too large.

  The hydroxyl value of the urea-modified polyester is usually 5 mgKOH / g or more, preferably 10 to 120 mgKOH / g, more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.

  In the present invention, the color toner may further contain a binder resin other than a resin having a urethane bond and / or a urea bond. The binder resin other than the resin having a urethane bond and / or a urea bond is not particularly limited, but includes a vinyl resin such as polyester, polyol resin, styrene-acrylic resin, epoxy resin, polycarbonate, polyurethane, and polyester unit. Examples include resins having at least two types of units, and two or more types may be used in combination.

  The colorant contained in the color toner is not particularly limited, but carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tart Rajin Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Red Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachloro Ortho Nitroani Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Poly Zored, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyani N, Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon, etc., may be used in combination.

  Examples of colorants for black include furnace black, lamp black, acetylene black, channel black and other carbon blacks (CI pigment black 7); copper, iron (CI pigment black 11), titanium oxide, and the like And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the colorant for magenta 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, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the colorant for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the colorant for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the color toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content of the colorant is less than 1% by mass, the coloring power of the color toner may be reduced. When the content exceeds 15% by mass, poor pigment dispersion occurs in the color toner and the coloring power is reduced. Or electrical characteristics may deteriorate.

  The colorant may be used as a master batch combined with a resin. Although it does not specifically limit as resin, Polymer of styrene or its derivative (s), such as a polystyrene, poly p-chlorostyrene, polyvinyltoluene; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene Copolymer, Styrene-vinyl naphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, Styrene- Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer Polymer, styrene-butadiene Styrene copolymers such as polymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polymethacrylic Acid butyl, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, unmodified polyester, resin having urethane bond and / or urea bond, epoxy resin, epoxy polyol resin, polyamide, polyvinyl butyral, polyacrylic acid, rosin, modified rosin Terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin and the like, and two or more kinds may be used in combination.

  The master batch is obtained by applying high shear force to the resin and the colorant and mixing or kneading. At this time, it is preferable to add an organic solvent in order to improve the interaction between the colorant and the resin. Moreover, since the wet cake of a coloring agent can be used as it is and it is not necessary to dry, it is preferable to use what is called a flushing method. The flushing method is a method of removing the water and the organic solvent after the colorant is transferred to the resin side by mixing or kneading the aqueous paste of the colorant together with the resin and the organic solvent. In addition, when mixing or kneading, it is preferable to use a high shear dispersion device such as a three-roll mill.

  In the present invention, the color toner may further contain a release agent, a charge control agent, a fluidity improving agent, a cleaning property improving agent, and the like, like the transparent toner of the present invention.

  In the present invention, the production method of the color toner is not particularly limited, and examples thereof include a pulverization method, a polymerization method, an emulsion aggregation method, a dissolution suspension method, a polyester elongation method, and a spray granulation method. Since a fine image is obtained, the dissolution suspension method, the polyester elongation method, and the spray granulation method are preferable.

  Hereinafter, as an example, a method for producing a color toner using a polyester stretching method will be described. In the polyester elongation method, a toner material containing an unmodified polyester, a prepolymer (A), an amino group-containing compound (B), a colorant, a release agent, a charge control agent and the like is dissolved or dispersed in an organic solvent. In the second liquid in which one liquid is dispersed in an aqueous medium, the prepolymer (A) and the compound (B) having an amino group are reacted, and then the organic solvent is removed, followed by filtration, washing and drying. This is a method for producing parent particles.

  The content of the prepolymer (A) in the toner material is usually 10 to 55% by mass, preferably 10 to 40% by mass, and more preferably 15 to 30% by mass.

  At this time, instead of adding a part of the toner material to the first liquid, the first liquid may be added after being dispersed in the aqueous medium. Specifically, when the compound (B) having an amino group is added after the first liquid is dispersed in an aqueous medium, the reaction between the prepolymer (A) and the compound (B) having an amino group is Since it starts from the interface, a concentration gradient of the urea-modified polyester can be formed inside the base particles. Moreover, you may add a coloring agent or a charge control agent to a base particle instead of adding to a 1st liquid. Specifically, the charge control agent may be driven into the base particles, or the base particles may be dyed.

  When ketimine, oxazoline, or the like is used instead of the compound (B) having an amino group, the compound (B) having an amino group is formed in an aqueous medium and can react with the prepolymer (A). .

  When the prepolymer (A) and the compound (B) having an amino group are reacted, the crosslinking degree and the molecular weight of the urea-modified polyester can be adjusted by using a terminator. At this time, after the first liquid containing the compound (B) having an amino group is dispersed in an aqueous medium and then adding a terminator, the reaction between the prepolymer (A) and the compound (B) having an amino group is caused. Since it is suppressed at the interface of the dispersed particles, a concentration gradient of the urea-modified polyester can be formed inside the base particles.

  As the terminator, monovalent amines such as diethylamine, dibutylamine, butylamine, laurylamine; ketimines blocked with amino groups of monovalent amines, oxazolines; n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isopentyl Examples thereof include monovalent alcohols such as alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, diphenyl alcohol, and triphenyl alcohol. Among them, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isopentyl alcohol, and n-hexyl alcohol are preferable because they are difficult to elute in an aqueous medium and easily remove an unreacted stopper.

  When the terminator is a monovalent alcohol, when adding the terminator, the equivalent ratio of the hydroxyl group of the monovalent alcohol to the isocyanate group of the prepolymer (A) is usually 0.01 to 1, 0.1-0.8 is preferable.

  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, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone, acetone and tetrahydrofuran, and two or more kinds may be used in combination. Of these, methyl acetate and ethyl acetate are preferred.

  The amount of the organic solvent used is usually 40 to 300 parts by weight, preferably 60 to 140 parts by weight, and more preferably 80 to 120 parts by weight with respect to 100 parts by weight of the toner material.

  As the aqueous medium, water or a mixed solvent of water and an aqueous solvent can be used. Examples of the aqueous solvent include, but are not limited to, alcohols such as methanol, isopropanol, and ethylene glycol; dimethylformamide; tetrahydrofuran; cellosolves such as methyl cellosolve; lower ketones such as acetone and methylethylketone; Good.

  In order to lower the viscosity of the aqueous medium in which the first liquid is dispersed, a solvent in which the prepolymer (A) is soluble may be added to the aqueous medium.

  The amount of the aqueous medium used is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the toner material. If the amount of the aqueous medium used is less than 50 parts by mass, the first liquid may not be uniformly dispersed, and if it exceeds 2000 parts by mass, it is disadvantageous in terms of cost.

  The aqueous medium may contain resin particles for the purpose of controlling the particle size of the base particles, improving granulation properties, and modifying the surface of the base particles.

  The average particle diameter of the resin particles is usually 5 to 200 nm, preferably 20 to 300 nm.

  The glass transition point of the resin particles is usually 40 to 90 ° C, preferably 50 to 70 ° C. When the glass transition point is less than 40 ° C., the storage stability of the color toner may be lowered, and when it exceeds 90 ° C., the low-temperature fixability of the color toner may be lowered.

  The weight average molecular weight of the resin particles is usually 4000 to 200000, preferably 4000 to 50000. When the weight average molecular weight is less than 4000, the storage stability of the color toner may be lowered, and when it exceeds 200,000, the low temperature fixability of the color toner may be lowered.

  The resin constituting the resin particles may be a thermoplastic resin or a thermosetting resin as long as it can be dispersed in an aqueous medium, but a styrene- (meth) acrylate copolymer or a styrene-butadiene copolymer. Vinyl resins such as polymers, (meth) acrylic acid-acrylic acid ester copolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers; epoxy resins Non-modified polyester, resin having urethane bond and / or urea bond, polyamide, polyimide, silicon-based resin, phenol resin, melamine resin, aniline resin, ionomer resin, polycarbonate, etc., may be used in combination of two or more . Among these, vinyl resins, polyurethanes, epoxy resins, and unmodified polyesters are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.

  Content of the resin particle in an aqueous medium is 0.5-10 mass% normally with respect to a 1st liquid from a granulation viewpoint, and 1-3 mass% is preferable.

  The surface coverage of the base particles by the resin particles is usually 1 to 90%, preferably 5 to 80%. When the surface coverage is less than 1%, the base particles may be easily aggregated. When the surface coverage exceeds 90%, the release agent existing inside the base particles is difficult to bleed out to the surface of the base particles. There is.

  The disperser used for dispersing the first liquid in the aqueous medium is not particularly limited, but is a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, an ultrasonic dispersion. Machine. Among them, a high-speed shearing disperser is preferable in order to make the dispersed particles have a particle diameter of 2 to 20 μm.

  When using a high-speed shearing disperser, the number of rotations is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. In the case of the batch method, the dispersion time is usually about 0.1 to 5 minutes. The dispersion temperature is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

  The aqueous medium may contain a surfactant. The surfactant is not particularly limited, but is an anionic surfactant such as alkylbenzene sulfonate, α-olefin sulfonate, and phosphate ester; alkylamine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, and the like. Amine salt type cationic surfactant; quaternary ammonium salt type cationic interface such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Activating agents; Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium beta Amphoteric surfactants such as emissions and the like.

  The dispersant is preferably a surfactant having a fluoroalkyl group. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and 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 and Its metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic 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 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC-129 (Manufactured by Sumitomo 3M); Unidyne DS-101, DS-102, (manufactured by Taikin Kogyo Co., Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large Nippon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary amines, secondary amines or secondary amine acids having a fluoroalkyl group, and aliphatics such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Quaternary ammonium salt; benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt 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.), MegaFuck F -150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and footent F-300 (manufactured by Neos).

  The aqueous medium may contain an inorganic compound dispersant that is hardly soluble in water. The inorganic compound dispersant is not particularly limited, and examples thereof include calcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  In addition, when using a compound soluble in acids or alkalis, such as calcium phosphate, it is preferable to remove from base particles by dissolving with an acid or an alkali and then washing with water. In addition, it can also be removed by decomposing with an enzyme.

  The aqueous medium may contain a polymeric protective colloid. The polymer-based protective colloid is not particularly limited, but acid groups such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, etc. Monomers having β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N-methylolacrylamide, N -(Meth) acrylic monomers having a hydroxyl group such as methylol methacrylamide; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; acrylamide, Methacrylamide, diacetone acrylamide and methylolated products thereof; acid chlorides of (meth) acrylic monomers such as acrylic acid chloride and methacrylic acid chloride; nitrogen atoms such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine or the like A homopolymer or a copolymer such as a monomer having a heterocyclic ring may be mentioned. Polymeric protective colloids include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include polyoxyethylenes such as oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester; and celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

  When removing the organic solvent from the second liquid, the temperature of the second liquid can be gradually raised to remove the organic solvent by evaporation. The second liquid can be sprayed into a dry atmosphere to remove the organic solvent and the aqueous medium. Although it does not specifically limit as dry atmosphere, The gas which heated air, nitrogen, a carbon dioxide gas, combustion gas etc. is mentioned, The various airflow heated to the temperature beyond the boiling point of the solvent contained in a 2nd liquid is preferable. At this time, when a spray dryer, a belt dryer, a rotary kiln or the like is used, the organic solvent and the aqueous medium can be removed in a short time.

  Next, after adding additives, such as a fluid improvement agent and a cleaning property improvement agent, to a base particle, it mixes and stirs using a mixer. Thereby, the surface of the base particle is coated while the additive is crushed, and a color toner is obtained.

  In the present invention, the color toner may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer. However, when applied to an ultrahigh-speed printing system that can handle POD. Is preferably a two-component developer from the viewpoint of improving the service life.

  As the carrier, the same toner as the transparent toner can be used, and the content of the color toner in the two-component developer is preferably 1 to 10% by mass with respect to the carrier.

  FIG. 1 shows an example of an image forming apparatus used in the present invention.

  The light source 11 irradiates a color original (not shown) with light, and the reflected light from the color original passes through a lens array 12 that divides and transmits an image. Next, reflected light is R (red), G (green), and B, which are the three primary colors of light, in an interline transfer CCD (color equivalent CCD) 13 that performs photoelectric conversion with a photodiode and performs accumulation and scanning. It is broken down into (blue) and detected. The RGB signals of the three primary colors created by the color equivalent CCD 13 are transmitted to an image processing unit (IPU) 14. Based on the RGB signals, the IPU 14 creates five color image signals of Bk (black), Y (yellow), M (magenta), C (cyan), and transparent. Next, the created Bk, Y, M, C and transparent image signals are transmitted to the writing unit 15. The writing unit 15 modulates and scans five laser beams for Bk, Y, M, C, and transparency, respectively, and sequentially forms an electrostatic latent image on the photosensitive drums 21, 22, 23, 24, and 25. Form. Here, the photosensitive drums 21, 22, 23, 24, and 25 correspond to Bk, Y, M, C, and transparency, respectively.

  Next, Bk, Y, M, and C color toner images and transparent toner images are formed on the photosensitive drums 21, 22, 23, 24, and 25, respectively, by the developing units 31, 32, 33, 34, and 35. Is done. At this time, the developing unit 35 can transfer the transparent toner image to a portion having a low density on the transfer paper by image calculation processing, or by designating an area, the entire transfer paper or the image portion can be specified. It is also possible to transfer the transparent toner image to the determined portion.

  On the other hand, after the transfer paper fed by the paper feeding unit 16 is conveyed on the transfer belt 70, the transfer drums 61, 62, 63, 64 and 65 sequentially transfer the photosensitive drums 21, 22, 23, 24 and 65. The Bk, Y, M, and C color toner images formed on 25 and the transparent toner image are transferred onto the transfer paper. Next, the transfer paper is conveyed to the fixing unit 80 to fix the toner image.

  On the other hand, the toner remaining on the photosensitive drums 21, 22, 23, 24, and 25 is removed by the cleaning members 41, 42, 43, 44, and 45, respectively. Next, after the photosensitive drums 21, 22, 23, 24, and 25 are charged by the charging members 51, 52, 53, 54, and 55, respectively, an electrostatic latent image is formed.

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

(Production of 50% by mass ethyl acetate solution of Prepolymer 1)
To a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, add 359 g of propylene oxide 2-mole adduct of bisphenol A, 22 g of adipic acid, 125 g of terephthalic acid, and 0.7 g of dibutyltin oxide, and a nitrogen atmosphere Under stirring, the temperature was raised to 230 ° C. and reacted for 10 hours, and then reacted for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg. Next, after cooling to 160 ° C., 17 g of phthalic anhydride was added and reacted for 2 hours. Further, after cooling to 80 ° C., 500 g of dehydrated ethyl acetate was added, and 95 g of isophorone diisocyanate was added with stirring and reacted for 2 hours to obtain Prepolymer 1. Next, ethyl acetate was added to obtain a 50% by mass ethyl acetate solution of Prepolymer 1.

  The prepolymer 1 had a number average molecular weight of 6500, a weight average molecular weight of 18000, a glass transition point of 55 ° C., and a free isocyanate content of 1.5% by mass.

(Production of urea-modified polyester 1)
In a four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, 400 g of a 50 mass% ethyl acetate solution of Prepolymer 1, a propylene oxide adduct of bisphenol A and a condensate of adipic acid (number average molecular weight) 800) 100 g, isophoronediamine 20 g, and ethyl acetate 50 g were added, the temperature was raised to 100 ° C. with stirring under a nitrogen atmosphere, and the reaction was allowed to proceed for 5 hours. Then, ethyl acetate was distilled off under reduced pressure, and urea-modified polyester 1 was obtained. Obtained. Urea-modified polyester 1 had a softening point of 104 ° C., a glass transition point of 60 ° C., an acid value of 18 KOH mg / g, and a hydroxyl value of 45 KOH mg / g.

(Manufacture of polyol resin 1)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 350 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-140P (manufactured by Mitsui Chemicals) having a number average molecular weight of 380 100 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-309 (manufactured by Mitsui Chemicals) with an average molecular weight of 3100, condensation of 320 g of bisphenol A, 80 g of p-cumylphenol, butylene oxide adduct of bisphenol A and adipic acid 110 g of a product (number average molecular weight 800) and 500 g of xylene were added, and the temperature was raised to 100 ° C. with stirring in a nitrogen atmosphere. Next, 0.2 g of lithium chloride was added, the temperature was raised to 160 ° C., and xylene was distilled off under reduced pressure. Furthermore, it was made to react until it reached a desired softening point, and the polyol resin 1 was obtained. Polyol resin 1 had a softening point of 103 ° C., a glass transition point of 62 ° C., an acid value of 2 KOH mg / g, a hydroxyl value of 85 KOH mg / g, and an epoxy equivalent of 2 × 10 ⁴ g / eq or more.

(Manufacture of polyol resin 2)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 240 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-140P (manufactured by Mitsui Chemicals) having a number average molecular weight of 380 250 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-309 (Mitsui Chemicals) having an average molecular weight of 3100, 220 g of bisphenol A, 120 g of propylene oxide adduct of bisphenol A, 80 g of p-cumylphenol, bisphenol A 150 g of a condensate of butylene oxide adduct and phthalic anhydride (number average molecular weight 1200) and 500 g of xylene were added, and the temperature was raised to 100 ° C. with stirring in a nitrogen atmosphere. Next, 0.2 g of lithium chloride was added, the temperature was raised to 160 ° C., and xylene was distilled off under reduced pressure. Furthermore, it was made to react until it reached a desired softening point, and the polyol resin 2 was obtained. Polyol resin 2 had a softening point of 105 ° C., a glass transition point of 62 ° C., an acid value of 4 KOH mg / g, a hydroxyl value of 60 KOH mg / g, and an epoxy equivalent of 2 × 10 ⁴ g / eq or more.

(Production of polyol resin 3)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 350 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-140P (manufactured by Mitsui Chemicals) having a number average molecular weight of 380 150 g of bisphenol A / epichlorohydrin type epoxy resin EPOMIK R-309 (manufactured by Mitsui Chemicals) having an average molecular weight of 3100, 150 g of bisphenol A, 120 g of propylene oxide adduct of bisphenol A, 80 g of p-cumylphenol, bisphenol A 50 g of a condensate of polypropylene oxide adduct and phthalic anhydride (number average molecular weight 1100) and 500 g of xylene were added, and the temperature was raised to 100 ° C. with stirring in a nitrogen atmosphere. Next, 0.2 g of lithium chloride was added, the temperature was raised to 160 ° C., and xylene was distilled off under reduced pressure. Furthermore, it was made to react until it reached a desired softening point, and the polyol resin 3 was obtained. Polyol resin 3 had a softening point of 102 ° C., a glass transition point of 64 ° C., an acid value of 5 KOH mg / g, a hydroxyl value of 26 KOH mg / g, and an epoxy equivalent of 2 × 10 ⁴ g / eq or more.

(Manufacture of polyurethane 1)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1000 g of toluene, 360 g of propylene oxide adduct of bisphenol A, 320 g of ethylene oxide adduct of bisphenol A, 35 g of 1,4-butanediol and After adding 560 g of isophorone diisocyanate and raising the temperature to 85 ° C. while stirring in a nitrogen atmosphere, 6 g of dioctyltin dilaurate was added and reacted for 10 hours, and toluene was distilled off under reduced pressure to obtain polyurethane 1. Polyurethane 1 had a softening point of 135 ° C., a glass transition point of 63 ° C., and a hydroxyl value of 12 KOH mg / g.

(Production of polyester 1)
Add 520 g of propylene oxide adduct of bisphenol A, 125 g of terephthalic acid, 80 g of itaconic acid, and 4 g of tin (II) 2-ethylhexanoate to a four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple. The solution was subjected to condensation polymerization at 230 ° C. for 10 hours while stirring in a nitrogen atmosphere, and then reacted at 230 ° C. for 1 hour under a reduced pressure of 8 kPa, and cooled to 220 ° C. Next, 140 g of trimellitic anhydride was added and reacted at normal pressure for 1 hour, and then reacted at 220 ° C. under a reduced pressure of 20 kPa until a desired softening point was reached to obtain polyester 1. Polyester 1 had a softening point of 102 ° C., a glass transition point of 59 ° C., an acid value of 16 KOH mg / g, and a hydroxyl value of 30 KOH mg / g.

(Softening point)
The softening point was measured using a flow tester CFT-500D (manufactured by Shimadzu Corporation). Specifically, while a 1 g sample is heated at a heating rate of 3 ° C./min, a load of 10 kg is applied by a plunger and extruded from a nozzle having a diameter of 0.5 mm and a length of 1 mm. The descending amount of the plunger of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was defined as the softening point.

(Glass transition point)
The glass transition point was measured using a differential scanning calorimeter DSC-60A (manufactured by Shimadzu Corporation). Specifically, an aluminum pan on which 0.01 to 0.02 g of a sample is placed is heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated at a heating rate of 10 ° C./min. The glass transition point of the intersection of the extended line of the base line below the maximum peak temperature of the endotherm and the tangent indicating the maximum inclination from the peak rising portion to the peak apex.

(Manufacture of master batch 1)
After mixing 1500 parts of water, 50 parts of carbon black Regal 400R (manufactured by Cabot), 50 parts of polyester RS801 (manufactured by Sanyo Chemical Industries) and 30 parts of water using a Henschel mixer (manufactured by Mitsui Mining), 2 Using this roll, melt kneading was performed at 160 ° C. for 50 minutes. The obtained kneaded product was rolled and cooled, and then pulverized using a pulverizer to obtain a black master batch 1.

  Further, instead of carbon black, C.I. I. Pigment Red 269, C.I. I. Pigment Blue 15: 2 and C.I. I. A magenta master batch 1, a cyan master batch 1, and a yellow master batch 1 were obtained in the same manner as the black master batch 1, except that Pigment Yellow 155 was used.

(Manufacture of master batch 2)
After mixing 1500 parts of water, 50 parts of carbon black Regal 400R (Cabot Corporation), 50 parts of polyol resin 1 and 30 parts of water using a Henschel mixer (Mitsui Mining Co., Ltd.), two rolls are used. The mixture was melt-kneaded at 160 ° C. for 50 minutes. The obtained kneaded product was rolled and cooled, and then pulverized using a pulverizer to obtain a black masterbatch 2.

  Further, instead of carbon black, C.I. I. Pigment Red 269, C.I. I. Pigment Blue 15: 2 and C.I. I. A magenta master batch 2, a cyan master batch 2 and a yellow master batch 2 were obtained in the same manner as the black master batch 2 except that Pigment Yellow 155 was used.

Example 1
A toner material comprising 92 parts of urea-modified polyester 1, 4 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. and 16 parts of black masterbatch 1 was added to a Henschel mixer FM10B (Mitsui The mixture was preliminarily mixed using Miike Kako Co., Ltd., and then melt kneaded at 100 to 130 ° C. using a biaxial kneader PCM-30 (Ikegai Co., Ltd.). Next, the kneaded product was cooled to room temperature, and then coarsely pulverized using a hammer mill so that the particle size became 200 to 300 μm. Further, the mixture was finely pulverized using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.) while adjusting the pulverization air pressure so that the weight average particle size was 4.9 to 5.5 μm. Next, using an air classifier MDS-I (manufactured by Nippon Pneumatic Industry Co., Ltd.), the weight average particle diameter is 5.8 to 6.2 μm, and the ratio of the weight average particle diameter to the number average particle diameter is 1.0 to Classification was performed while adjusting the louver opening so as to be 1.2 to obtain base particles.

  100 parts of base particles and 1.0 part of hydrophobic silica HDK-2000 (manufactured by Clariant) were stirred and mixed using a Henschel mixer to obtain a black toner.

  450 parts of toluene, 450 parts of silicone resin SR2400 (manufactured by Toray Dow Corning Silicone) with a nonvolatile content of 50% by weight, 10 parts of aminosilane SH6020 (manufactured by Toray Dow Corning Silicone) and 10 parts of carbon black, And dispersed for 10 minutes to obtain a coating solution. The obtained coating solution and 5000 parts of Cu—Zn ferrite particles having a weight average particle size of 55 μm are put into a coating apparatus for coating while forming a swirling flow in which a rotating bottom plate disk and a stirring blade are provided in a fluidized bed. Then, a coating solution was applied to the Cu—Zn ferrite particles. The Cu—Zn ferrite particles coated with the coating solution were baked at 280 ° C. for 2 hours using an electric furnace to obtain a carrier.

  5 parts of black toner and 95 parts of carrier were mixed for 5 minutes at 48 rpm using a tumbler mixer (made by Willy et Bacofen (WAB) Co., Ltd.) of a type in which the container was rolled and stirred, and a black developer Got.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 1, a cyan master batch 1 and a yellow master batch 1 are used instead of the black master batch 1. Got.

  A transparent developer was prepared in the same manner as the black developer, except that 100 parts of polyol resin 1 and 6 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. were used as toner materials. Obtained.

(Number average particle size and weight average particle size)
The number average particle size and the weight average particle size were measured using a Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter, Inc.) Was used for analysis. Specifically, first, 10 mg of base particles are added to 5 ml of an electrolytic solution Isoton II (manufactured by Beckman Coulter) containing 5% by mass of Emulgen 109P (manufactured by Kao Corporation) of polyoxyethylene lauryl ether having an HLB of 13.6, After dispersing for 1 minute using an ultrasonic disperser, 25 ml of electrolyte solution Isoton II (manufactured by Beckman Coulter, Inc.) was added, and the mixture was dispersed for 1 minute using an ultrasonic disperser. Next, 100 ml of the obtained dispersion and electrolyte Isoton II (manufactured by Beckman Coulter) are added to a beaker, and the particle size of 30,000 particles is such that the particle size of 30,000 particles can be measured in 20 seconds. The number average particle size and the weight average particle size were determined. In addition,
(Example 2)
Water dispersion (Sanyo Kasei Kogyo Co., Ltd.) of 100 parts of water and a vinyl resin having a solid content of 20% by mass (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct) 10 parts), 50 parts by weight of an aqueous 50% by weight solution of sodium dodecyl diphenyl ether disulfonate, eleminol MON-7 (manufactured by Sanyo Chemical Industries), 40 parts of a 1% by weight aqueous solution of carboxymethylcellulose cellogen BSH (manufactured by Sanyo Chemical Industries) and acetic acid 15 parts of ethyl was mixed and stirred to obtain a milky white dispersion medium.

  500 parts of urea-modified polyester 1, 40 parts of carnauba wax and 200 parts of ethyl acetate are charged into a container equipped with a stir bar and a thermometer, heated to 80 ° C. with stirring and held for 5 hours, then 1 hour. At 30 ° C. Next, using an ultra visco mill (made by Imex Co., Ltd.) of a bead mill, 80% by volume of zirconia beads having a particle diameter of 0.5 mm at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / second, Dispersion was performed under conditions of 5 passes.

  740 parts of the resulting dispersion, 420 parts of urea-modified polyester 1, 160 parts of black masterbatch 1 and 100 parts of ethyl acetate were added to a vessel equipped with a stirring bar and a thermometer, and an ultra visco mill (IMEX Co., Ltd.), a bead mill. Manufactured), zirconia beads having a particle diameter of 0.5 mm and 80 volume% were filled at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / second, and dispersed under conditions of 5 passes.

  1420 parts of the obtained dispersion liquid, 1420 parts of dispersion medium, and 5 parts of an emulsion stabilizer UCAT660M (manufactured by Sanyo Chemical Industries) are put in a container, and at 28 ° C., 9000 rpm using a TK homomixer (manufactured by Special Machinery Corporation). For 30 minutes to obtain an emulsified slurry.

  The obtained emulsified slurry was put into a container equipped with a stirrer and a thermometer, the organic solvent was distilled off at 35 ° C. for 10 hours, and then aged at 45 ° C. for 12 hours to obtain a slurry.

  After filtering 100 parts of the resulting slurry under reduced pressure, 300 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer and filtered under reduced pressure. Next, 100 parts of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer, followed by filtration under reduced pressure. Further, 100 parts of 10 mass% hydrochloric acid was added to the filter cake, and the mixture was stirred at 6000 rpm for 15 minutes using a TK homomixer, and then filtered under reduced pressure. Next, 500 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred at 6000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.

  The obtained filter cake was dried at 40 ° C. for 24 hours using a circulating dryer, sieved with a mesh having an opening of 75 μm, a weight average particle size of 5.0 μm, and a weight average particle size with respect to the number average particle size. Mother particles having a ratio of 1.13 was obtained.

  100 parts of base particles and 1.0 part of hydrophobic silica HDK-2000 (manufactured by Clariant) were stirred and mixed using a Henschel mixer to obtain a black toner.

  5 parts of black toner and 95 parts of carrier were mixed for 5 minutes at 48 rpm using a tumbler mixer (made by Willy et Bacofen (WAB) Co., Ltd.) of a type in which the container was rolled and stirred, and a black developer Got.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 1, a cyan master batch 1 and a yellow master batch 1 are used instead of the black master batch 1. Got.

  A transparent developer was obtained in the same manner as in Example 1.

(Example 3)
Water dispersion (Sanyo Kasei Kogyo Co., Ltd.) of 100 parts of water and a vinyl resin having a solid content of 20% by mass (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct) 10 parts), 50 parts by weight of an aqueous 50% by weight solution of sodium dodecyl diphenyl ether disulfonate, eleminol MON-7 (manufactured by Sanyo Chemical Industries), 40 parts of a 1% by weight aqueous solution of carboxymethylcellulose cellogen BSH (manufactured by Sanyo Chemical Industries) and acetic acid 15 parts of ethyl was mixed and stirred to obtain a milky white dispersion medium.

  In a container in which a stir bar and a thermometer are set, 250 parts of polyester (manufactured by Sanyo Chemical Co., Ltd.) having a number average molecular weight of 5700 and a glass transition point of 50 ° C., 40 parts of carnauba wax and 200 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., held for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, using an ultra visco mill (made by Imex Co., Ltd.) of a bead mill, 80% by volume of zirconia beads having a particle diameter of 0.5 mm at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / second, Dispersion was performed under conditions of 5 passes.

  490 parts of the obtained dispersion liquid, 520 parts of polyester (manufactured by Sanyo Chemical Industries) having a number average molecular weight of 5700 and a glass transition point of 50 ° C., 160 parts of black masterbatch 1 and 100 parts of ethyl acetate, stirring rod and temperature In addition to the container in which the meter is set, using a bead mill, Ultra Visco Mill (manufactured by Imex), 80 zirconia beads having a particle diameter of 0.5 mm at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / sec. The solution was filled in volume% and dispersed under the condition of 5 passes.

  1270 parts of the resulting dispersion, 1420 parts of dispersion medium, 150 parts of 50% by weight ethyl acetate solution of Prepolymer 1, 1 part of isobutyl alcohol, 7 parts of isophoronediamine and 5 parts of an emulsion stabilizer UCAT660M (manufactured by Sanyo Chemical Industries) The mixture was placed in a container and dispersed at 9000 rpm for 30 minutes at 28 ° C. using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.).

  The obtained dispersion was heated to 58 ° C. and dispersed at 1500 rpm for 1 hour using a TK homomixer to obtain an emulsified slurry.

  The obtained emulsified slurry was put into a container equipped with a stirrer and a thermometer, the organic solvent was distilled off at 35 ° C. for 10 hours, and then aged at 45 ° C. for 12 hours to obtain a slurry.

  After filtering 100 parts of the resulting slurry under reduced pressure, 300 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer and filtered under reduced pressure. Next, 100 parts of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer, followed by filtration under reduced pressure. Further, 100 parts of 10% by mass hydrochloric acid was added to the filter cake, and the mixture was stirred at 6000 rpm for 15 minutes using a TK homomixer, and then filtered under reduced pressure. Next, 500 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred at 6000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.

  The obtained filter cake was dried at 40 ° C. for 24 hours using a circulating dryer, sieved with a mesh having an opening of 75 μm, a weight average particle size of 5.2 μm, and a weight average particle size of the number average particle size. Base particles having a ratio of 1.14 were obtained.

  100 parts of base particles and 1.0 part of hydrophobic silica HDK-2000 (manufactured by Clariant) were stirred and mixed using a Henschel mixer to obtain a black toner.

  5 parts of black toner and 95 parts of carrier were mixed for 5 minutes at 48 rpm using a tumbler mixer (made by Willy et Bacofen (WAB) Co., Ltd.) of a type in which the container was rolled and stirred, and a black developer Got.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 1, a cyan master batch 1 and a yellow master batch 1 are used instead of the black master batch 1. Got.

  A transparent developer was obtained in the same manner as in Example 1.

Example 4
In the same manner as in Example 3, a black developer, a magenta developer, a cyan developer, and a yellow developer were obtained.

  A transparent developer was prepared in the same manner as in Example 1 except that 100 parts of polyol resin 2 and 6 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. were used as toner materials. Obtained.

(Example 5)
In the same manner as in Example 3, a black developer, a magenta developer, a cyan developer, and a yellow developer were obtained.

  A transparent developer was prepared in the same manner as in Example 1 except that 100 parts of polyol resin 3 and 6 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. were used as toner materials. Obtained.

(Example 6)
Except for using 92 parts of polyurethane 1, paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) 4 parts and 16 parts of black masterbatch 1 as the toner material, the same as Example 1 Thus, a black developer was obtained.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 1, a cyan master batch 1 and a yellow master batch 1 are used instead of the black master batch 1. Got.

  A transparent developer was obtained in the same manner as in Example 1.

(Comparative Example 1)
In the same manner as in Example 1, a black developer, a magenta developer, a cyan developer, and a yellow developer were obtained.

  A transparent developer in the same manner as in Example 1 except that 100 parts of urea-modified polyester 1 and 6 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. were used as toner materials. Got.

(Comparative Example 2)
In the same manner as in Example 1, a black developer, a magenta developer, a cyan developer, and a yellow developer were obtained.

  A transparent developer was obtained in the same manner as in Example 1 except that 100 parts of polyester 1 and 6 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 76.1 ° C. were used as toner materials. It was.

(Comparative Example 3)
In the same manner as in Example 3, a black developer, a magenta developer, a cyan developer, and a yellow developer were obtained.

  Water dispersion (Sanyo Kasei Kogyo Co., Ltd.) of 100 parts of water and a vinyl resin having a solid content of 20% by mass (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct) 10 parts), 50 parts by weight of an aqueous 50% by weight solution of sodium dodecyl diphenyl ether disulfonate, eleminol MON-7 (manufactured by Sanyo Chemical Industries), 40 parts of a 1% by weight aqueous solution of carboxymethylcellulose cellogen BSH (manufactured by Sanyo Chemical Industries) and acetic acid 15 parts of ethyl was mixed and stirred to obtain a milky white dispersion medium.

  In a container in which a stir bar and a thermometer are set, 250 parts of polyester (manufactured by Sanyo Chemical Co., Ltd.) having a number average molecular weight of 5700 and a glass transition point of 50 ° C., 40 parts of carnauba wax and 200 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., held for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, using an ultra visco mill (made by Imex Co., Ltd.) of a bead mill, 80% by volume of zirconia beads having a particle diameter of 0.5 mm at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / second, Dispersion was performed under conditions of 5 passes.

  490 parts of the obtained dispersion, number average molecular weight 5700, glass transition point 50 ° C. polyester (manufactured by Sanyo Kasei Kogyo Co., Ltd.) 600 parts and ethyl acetate 100 parts are added to a vessel equipped with a stirring bar and a thermometer, Using a bead mill, Ultra Visco Mill (manufactured by Imex), 80% by volume of zirconia beads having a particle diameter of 0.5 mm were filled at a liquid feeding speed of 1.2 kg / hour, a disk peripheral speed of 10 m / second, and a number of passes of 5 It was dispersed under the conditions of the times.

  1270 parts of the resulting dispersion, 1420 parts of dispersion medium, 150 parts of 50% by weight ethyl acetate solution of Prepolymer 1, 1 part of isobutyl alcohol, 7 parts of isophoronediamine and 5 parts of an emulsion stabilizer UCAT660M (manufactured by Sanyo Chemical Industries) The mixture was placed in a container and dispersed at 9000 rpm for 30 minutes at 28 ° C. using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.).

  The obtained dispersion was heated to 58 ° C. and dispersed at 1500 rpm for 1 hour using a TK homomixer to obtain an emulsified slurry.

  The obtained emulsified slurry was put into a container equipped with a stirrer and a thermometer, the organic solvent was distilled off at 35 ° C. for 10 hours, and then aged at 45 ° C. for 12 hours to obtain a slurry.

  After filtering 100 parts of the resulting slurry under reduced pressure, 300 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer and filtered under reduced pressure. Next, 100 parts of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake, and the mixture was stirred for 15 minutes at 6000 rpm using a TK homomixer, followed by filtration under reduced pressure. Further, 100 parts of 10% by mass hydrochloric acid was added to the filter cake, and the mixture was stirred at 6000 rpm for 15 minutes using a TK homomixer, and then filtered under reduced pressure. Next, 500 parts of ion-exchanged water was added to the filter cake, and the mixture was stirred at 6000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.

  The obtained filter cake was dried at 40 ° C. for 24 hours using a circulating dryer, sieved with a mesh having an opening of 75 μm, a weight average particle size of 5.2 μm, and a weight average particle size of the number average particle size. Base particles having a ratio of 1.14 were obtained.

  100 parts of base particles and 1.0 part of hydrophobic silica HDK-2000 (manufactured by Clariant) were stirred and mixed using a Henschel mixer to obtain a transparent toner.

  A transparent developer was obtained in the same manner as in Example 1 except that the obtained transparent toner was used.

(Comparative Example 4)
Example 1 except that 92 parts of polyol resin 1, 4 parts of paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) and 16 parts of black masterbatch 2 were used as toner materials. Similarly, a black developer was obtained.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 2, a cyan master batch 2 and a yellow master batch 2 are used instead of the black master batch 2. Got.

  A transparent developer was obtained in the same manner as in Example 1.

(Comparative Example 5)
Except for using 92 parts of polyester 1, paraffin wax HNP-9 (manufactured by Nippon Seiwa Co., Ltd.) 4 parts and 16 parts of black masterbatch 1 as the toner material, the same as in Example 1. Thus, a black developer was obtained.

  Further, a magenta developer, a cyan developer and a yellow developer are respectively used in the same manner as the black developer except that a magenta master batch 1, a cyan master batch 1 and a yellow master batch 1 are used instead of the black master batch 1. Got.

  A transparent developer was obtained in the same manner as in Example 1.

(Image evaluation)
The following image evaluation was performed using the image forming apparatus of FIG.

[Image graininess and sharpness]
In full color mode, output a test chart including full color photographic images, text images, solid images of black, cyan, magenta, yellow, red, green, and blue to POD gloss coated paper (manufactured by Oji Paper Co., Ltd.), transparent toner The degree of granularity and sharpness of the image not using the toner and the image overcoated with the transparent toner placed on the entire test chart were visually evaluated. It should be noted that the degree of granularity and sharpness of the image is 5 when it is equivalent to offset printing, 4 is slightly better than the conventional electrophotographic image, 3 is the conventional electrophotographic image, and 3 Judgment was made with 2 being slightly worse than the electrophotographic image and 1 being considerably worse than the conventional electrophotographic image.

[Transfer Chile]
In full color mode, output a test chart including full color photographic images, text images, solid images of black, cyan, magenta, yellow, red, green, and blue to POD gloss coated paper (manufactured by Oji Paper Co., Ltd.), transparent toner The frequency and extent of transfer dust in images that did not use toner and images overcoated with transparent toner over the entire test chart were evaluated by comparison with step samples. Note that 5 is the case where transfer dust is not seen at all, 4 is the case where very slight transfer dust is seen at a low frequency, 3 is the case where the frequency and degree of transfer dust is about the same as a conventional electrophotographic image, Judgment was made on the assumption that the occurrence frequency of dust was high and the level was 2 and the transfer dust was generated at a high frequency and the level was 1 as bad.

[Change rate of haze degree]
In full color mode, solid images of cyan, magenta and yellow (toner adhesion amount 0.40 ± 0.1 mg / cm ² ) were output to an OHP sheet type PPC-DX (manufactured by Ricoh) at a fixing temperature of 160 ° C. . At this time, the haze degree Hc of the image not using the transparent toner and the haze degree Ht of the image overcoated with the transparent toner of 0.40 ± 0.1 mg / cm ² over the entire solid image are directly read. Measurement was performed using a computer HGM-2DP type (manufactured by Suga Test Instruments Co., Ltd.), and the change rate of the haze degree when the transparent toner was placed was determined. The haze degree is also referred to as haze, and is used as a scale indicating the transparency of the toner. The smaller the value, the higher the transparency, and the better the color developability when an OHP sheet is used. The change rate of the haze degree is expressed by the formula | Ht−Hc |
The larger the value, the greater the change in the haze degree when the transparent toner is placed.

[Changes in color reproducibility]
In the full color mode, cyan, magenta and yellow solid images (toner adhesion amount 0.40 ± 0.1 mg / cm ² ) were output to POD gloss coated paper (manufactured by Oji Paper Co., Ltd.). At this time, the La ^* b ^* value (L (c), a (c), b (c)) in the CIE La ^* b ^* color space of the image not using the transparent toner and 0.40 ± 0 . La ^* b ^* values in the CIE La ^* b ^* color space of the image overcoated with 1 mg / cm ² of transparent toner over the entire image (referred to as L (t), a (t), b (t)) Was measured using a spectral densitometer X-Rite 938 (manufactured by X-Rite) to determine the color difference ΔE. ΔE is expressed by the formula [{L (t) −L (c)} ² + {(t) −a (c)} ² + {b (t) −b (c)} ² ] ^0.5
The larger the value, the greater the variation in color reproducibility when the transparent toner is placed.

表１より、実施例の透明トナーと、ウレタン結合及び／又はウレア結合を有する樹脂を含むカラートナーの組み合わせは、ヘイズ度の低下及び色再現性の変動を抑制できることに加え、転写チリの発生を抑制できることがわかる。

From Table 1, the combination of the transparent toner of the example and the color toner containing a resin having a urethane bond and / or a urea bond can suppress the decrease in haze and the variation in color reproducibility, and also the generation of transfer dust. It turns out that it can suppress.

11 Light source 12 Lens array 13 Interline transfer CCD
14 Image processing unit 15 Writing unit 21, 22, 23, 24, 25 Photosensitive drum 31, 32, 33, 34, 35 Developing unit 41, 42, 43, 44, 45 Cleaning member 51, 52, 53, 54, 55 Charging member 61, 62, 63, 64, 65 Transfer charger 70 Transfer belt 80 Fixing unit

JP-A-3-237468

Claims (10)

A toner set having color toner and transparent toner,
The color toner is seen containing a resin having a urethane bond and / or a urea bond, a colorant,
The transparent toner contains a polyol resin, does not contain a colorant ,
The polyol resin is at least an epoxy resin, dihydric phenol and a divalent alkylene oxide adducts of phenols and toner set, characterized in that it is obtained by reacting a resin obtained by condensing a polycarboxylic acid. The epoxy resin has a general formula

(In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms, and k and n are each independently 0 or 1; , L is an integer from 1 to 10, and m is an integer from 0 to 120, except when m and n are 0.)
The toner set according to claim 1, wherein the toner set is represented by the formula: The toner set according to claim 1, wherein the dihydric phenol is bisphenol A. The resin obtained by condensing the alkylene oxide adduct of dihydric phenol and polyvalent carboxylic acid has the general formula

(In the formula, R ² is an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms, and o and p are each independently 0 or more and 200 or less. Integer, except when o and p are 0.
The toner set according to any one of claims 1 to 3, characterized in that in a resin represented. 5. The toner set according to claim 1, wherein the polyol resin has a hydroxyl value of 25 KOHmg / g or more and 60 KOHmg / g or less. The toner set according to claim 1, wherein the polyol resin has an epoxy equivalent of 2 × 10 ⁴ g / eq or more. The toner set according to claim 1, wherein the resin having a urethane bond and / or a urea bond is a urea-modified polyester. The toner set according to claim 1, wherein the color toner is manufactured using a dissolution suspension method or a polyester elongation method. A developer set having a developer containing a color toner and a developer containing a transparent toner,
The color toner includes a resin having a urethane bond and / or a urea bond, and a colorant.
The transparent toner contains a polyol resin, does not contain a colorant,
The polyol resin is at least an epoxy resin, dihydric phenol and a divalent alkylene oxide adduct of phenol and developer set, characterized in that it is obtained by the polycarboxylic acid is reacted with a resin obtained by condensing . Image forming apparatus and forming an image using the developer set forth in 請 Motomeko 9.

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