JP5655548B2 - Toner manufacturing method, toner, developer, and image forming apparatus - Google Patents

Description

The present invention relates to a method for producing a preparative toner, the toner, a developing agent and an image forming apparatus.

  Image formation by electrophotography generally involves forming an electric latent image on a photoconductor produced using a photoconductive substance by various means, and then developing the latent image with a developer, and then developing the image. The image formed by the agent is transferred onto paper or the like as necessary, and further fixed by heating, pressurization, solvent vapor, or the like.

  In recent years, in order to save energy by fixing toner at a low temperature, the thermal energy given to the toner during fixing tends to be small. For this reason, it is considered that lowering the toner fixing temperature is an essential technical achievement.

  In order to cope with such low-temperature fixing, attempts have been made to use polyester resins in place of vinyl resins that have been widely used as binder resins. In addition, there is an attempt to use crystalline polyester for the purpose of improving low-temperature fixability (Patent Document 1), but the compatibility with heat-resistant storage stability is insufficient.

The present invention maintains a high heat-resistant storage stability, and to provide a manufacturing how excellent For toner to the low-temperature fixability.

According to the present invention, a compound containing an active hydrogen group, a polymer having a group capable of reacting with the active hydrogen group, a colorant, and a material containing a release agent are dissolved or dispersed in an organic solvent to form the first. A step of obtaining a liquid, a step of emulsifying or dispersing the first liquid in an aqueous medium containing fine particles of polyurethane resin, and obtaining the second liquid, and removing the organic solvent from the second liquid. And a process for producing a toner, wherein the polyurethane-based resin is obtained by reacting a crystalline polyester diol, a diisocyanate, and a diol having a carboxyl group and then neutralizing .

According to the present invention, to maintain a high heat-resistant storage stability, it can provide a manufacturing how excellent For toner to the low-temperature fixability.

  The present invention is described in detail below.

The toner of the present invention has a polyurethane resin on the surface of base particles containing an amorphous polyester resin, a colorant, and a release agent, and the polyurethane resin is a diol having a crystalline polyester diol, a diisocyanate, and a carboxyl group. After the reaction, the polyurethane resin is obtained by neutralization. Thereby, it is possible to provide a toner that maintains high heat-resistant storage stability and is excellent in low-temperature fixability.
(Polyurethane resin)
The polyurethane resin used in the present invention can be obtained by reacting a crystalline polyester diol, a diisocyanate compound and a diol having a carboxyl group by a known method and then neutralizing. When the crystalline polyester diol, the diisocyanate compound and the diol having a carboxyl group are reacted, it is preferable to adjust the molecular weight using a known molecular weight regulator.

  When the polyurethane resin fine particles to be described later are produced using amorphous polyester diol instead of crystalline polyester diol, the resulting polyurethane resin fine particles have high solubility in the solvent, and the base particles are being granulated. The polyurethane resin fine particles are eluted into the solvent, and it becomes difficult for the polyurethane resin fine particles to be present on the surface of the base particles. Therefore, it is desirable to use a crystalline polyester diol.

  The acid value of the polyurethane resin before neutralization is preferably 15 to 40 mgKOH / g. When the acid value of the polyurethane resin is less than 15 mgKOH / g, the polyurethane resin fine particles are not self-dispersed in an aqueous medium described later, which is not preferable. Moreover, when the acid value of the polyurethane resin exceeds 40 mgKOH / g, the crystallinity of the polyurethane resin may not be exhibited.

  The mixing ratio of the crystalline polyester diol, diisocyanate, and carboxyl group-containing diol is preferably such that NCO / OH is within the range of 0.7 to 0.95. Here, NCO is the molar amount of the isocyanate group, and OH is the molar amount of the hydroxyl group of the crystalline polyester diol and the diol having a carboxyl group. When NCO / OH is smaller than 0.7, the molecular weight of the polyurethane resin becomes small, and it may be difficult to ensure granulation / storability. In addition, when NCO / OH exceeds 0.95, the molecular weight is too large, and it may be difficult to produce polyurethane fine particles.

(Crystalline polyester diol)
The crystalline polyester diol can be obtained by subjecting an aliphatic diol and an aliphatic dicarboxylic acid to known dehydration condensation polymerization. Examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- Examples include decanediol, 1,12-dodecanediol, 1,20-eicosanediol, and the like. Examples of the aliphatic carboxylic acid include oxalic acid, adipic acid, azelaic acid, sebacic acid, 1,16-hexadecanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,20-eicosanedicarboxylic acid, maleic acid, fumar An acid etc. are mentioned.

  The average molecular weight of the crystalline polyester is preferably 2000 to 10,000. If the average molecular weight of the crystalline polyester is less than 2000, the resulting polyurethane may have low crystallinity. Moreover, when the average molecular weight of crystalline polyester exceeds 10,000, the melt viscosity of a polyurethane resin may become high and it may become difficult to obtain microparticles | fine-particles.

The melting point of the crystalline polyester diol is preferably 65 to 100 ° C. When the melting point of the crystalline polyester diol is 65 ° C. or less, the heat resistant storage stability of the toner may be adversely affected. When the melting point of the crystalline polyester diol is 100 ° C. or higher, the low-temperature fixability of the toner may be deteriorated.
(Diisocyanate)
Examples of the diisocyanate include 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4, 4′-dibenzyl diisocyanate, tetraalkyldiphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bi-isocyanate (Isosa sulphonate) cyclohexane, methylcyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, and carbodiimides diphenylmethane diisocyanate.
(Diol having a carboxyl group)
Examples of the diol having a carboxyl group include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolalkanoic acid such as dimethylolpentanoic acid, dihydroxyaliphatic dicarboxylic acid such as dihydroxysuccinic acid, and dihydroxybenzoic acid. And the like, and the like.
(Neutralizer)
Examples of the neutralizing agent for neutralizing the polyurethane resin include monoamines such as diethylamine, dibutylamine, butylamine, and laurylamine.
(Molecular weight regulator)
Examples of the molecular weight modifier include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

In the present invention, it is preferable to contain at least the following amorphous polyester resin as a binder resin for the toner. The amorphous polyester resin includes a modified polyester resin and an unmodified polyester resin, and it is more preferable to contain both.
(Modified polyester resin)
The modified polyester can be obtained by reacting a compound having an active hydrogen group with a polymer having a group capable of reacting with the active hydrogen group. In the present invention, the following urea-modified polyester resins can be used.
(Polymer having a group capable of reacting with an active hydrogen group)
In the present invention, a polyester prepolymer having an isocyanate group can be used as the polymer having a group capable of reacting with an active hydrogen group. Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the urea content in the urea-modified polyester is lowered, and the hot offset resistance is deteriorated. The content of the polyisocyanate (3) component in the polyester prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.
(Compound having an active hydrogen group)
In the present invention, amines can be used as the compound having an active hydrogen group. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, the molecular weight of the urea-modified polyester after completion of the reaction can be adjusted by using a terminator if necessary. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).
The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/1 to 2/1, preferably 1/1 to 1.5 / 1, more preferably 1/1 to 1.2 / 1. When [NCO] / [NHx] is larger than 2, the molecular weight of the urea-modified polyester (i) is lowered, and the hot offset resistance is deteriorated.
(Unmodified polyester)
In the present invention, not only the polyester prepolymer (A) having an isocyanate group is used alone but also an unmodified polyester (C) is contained as a toner binder component together with the polyester prepolymer (A) having an isocyanate group. It is more preferable. By using the unmodified polyester (C) in combination, the low-temperature fixability and the glossiness and gloss uniformity when used in a full-color apparatus are improved. Examples of the unmodified polyester (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as those of the polyester component of the polyester prepolymer (A) having an isocyanate group. The same as the polyester prepolymer (A) having an isociate group. In addition, it is preferable in terms of low-temperature fixability and hot offset resistance that the polyester prepolymer (A) having an isocyanate group and the unmodified polyester (C) are at least partially compatible. Therefore, the polyester component of the polyester prepolymer (A) having an isocyanate group and the unmodified polyester (C) preferably have similar compositions. When the unmodified polyester (C) is contained, the weight ratio of the prepolymer (A) having an isocyanate group to the unmodified polyester (C) is usually 5/95 to 75/25, preferably 10/90 to 25 / 75, more preferably 12/88 to 25/75, and particularly preferably 12/88 to 22/78. When the weight ratio of the polyester prepolymer (A) having an isocyanate group is less than 5% by mass, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight of the unmodified polyester (C) is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of the unmodified polyester (C) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and particularly preferably 20 mgKOH / g to 80 mgKOH / g. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of the unmodified polyester (C) is usually 0.5 mgKOH / g to 40 mgKOH / g, preferably 5 mgKOH / g to 35 mgKOH / g. By giving the acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.
(Coloring agent)
As the colorant of the present invention, known dyes and pigments can be appropriately used. For example, 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), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline 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 , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. Examples of the binder resin kneaded together with the master batch include the above-described urea-modified polyester resin and non-modified polyester resin, and polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene- p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene 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-chloromethacrylate Methyl acid copolymer, steel -Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Examples thereof include acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and can also be used in mixture of 2 or more types.

This master batch can be obtained by mixing and kneading the master batch resin and the colorant with high shearing force to obtain a master batch. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method, which is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing water and organic solvent components, is also used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.
(Release agent)
The wax of the present invention can be appropriately selected from known ones. For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. can be mentioned. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among the carbonyl group-containing waxes, polyalkanoic acid esters are preferable. The melting point of the wax of the present invention is usually from 40 ° C to 160 ° C, preferably from 50 ° C to 120 ° C, more preferably from 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 1000 cps, as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0% to 40% by weight, preferably 3% to 30% by weight.
(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst AG), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine , Perylene, quinacridone, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. is not. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, the range of 0.2 mass part-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, so that the effect of the main charge control agent is diminished and the electrostatic attractive force with the developing roller is increased. As a result, the fluidity of the developer is lowered and the image density is lowered. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or they can be added when directly dissolving or dispersing in an organic solvent, or toner particles can be fixed on the toner surface after preparation. May be.
(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the toner obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 200 nm, and particularly preferably 10 nm to 100 nm. Moreover, it is preferable that the specific surface area of the particle | grains measured by BET method is 20-500 m < ² > / g. The amount of the inorganic fine particles used is preferably 0.01% to 5% by weight of the toner weight, and particularly preferably 0.01% to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

Examples of the cleaning performance improver for removing the developer after transfer remaining on the photoreceptor or primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 μm to 1 μm.
(Average circularity and circularity distribution)
The average circularity E of the toner is defined by the circularity E = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. The circularity was measured by an optical detection band method in which a suspension containing particles was passed through an imaging unit detection band on a flat plate, and a particle image was optically detected and analyzed by a CCD camera. The toner of the present invention was measured by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). A specific measurement method will be described later.

It is important that the toner in the present invention has a specific shape and shape distribution, and the average circularity of the toner is less than 0.95, and the toner having an irregular shape that is too far from the spherical shape has low transferability. Therefore, there is a high possibility that dust will remain on the image quality image obtained by using the image forming apparatus with toner. That is, it has been found that toner having an average circularity in the range of 1.00 to 0.95 is effective for forming a high-definition image having appropriate density reproducibility.
(Dv / Dn (ratio of volume average particle diameter to number average particle diameter))
The volume average particle diameter (Dv) of the toner is 3 μm to 8 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.05 to 1.25, preferably When the toner is in the range of 1.10 to 1.25, the toner is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance. In particular, the glossiness of the image is excellent when used in a full-color copying machine or the like. Further, in the two-component developer using the toner, even when the toner balance is performed for a long time, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable development performance can be obtained. Furthermore, even when the toner is used as a one-component developer, even when the balance of the toner is performed over a long period of time, the toner particle diameter variation is reduced, and the toner filming on the developing roller, The fusion of toner to a member such as a blade for thinning the toner is reduced. As a result, a good and stable image can be obtained even when the toner is used for a long time in a developing device.

  Generally, it is said that the smaller the toner particle size, the higher the resolution and the higher the quality of the image obtained after development. On the other hand, it is disadvantageous that the toner particle size is small for the transferability of the toner and the cleaning properties for removing the residual developer after the transfer. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier. When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

  On the other hand, when the particle size of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size fluctuates greatly as the balance of the toner is performed. There are many cases. The same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

Further, when the volume average particle diameter / number average particle diameter is smaller than 1.05, it is preferable in terms of stable toner behavior and uniform toner charge amount. However, there are cases where the toner becomes insufficiently charged, and the cleaning property of the developer may deteriorate.
(Toner production method)
In the toner production method of the present invention, a toner material containing a compound having an active hydrogen group, a polymer having a group capable of reacting with the active hydrogen group, a colorant, and a release agent is dissolved or dispersed in an organic solvent. A step, emulsifying or dispersing the dispersion obtained in the step in an aqueous medium containing polyurethane resin fine particles, the compound having an active hydrogen group, and a weight having a group capable of reacting with the active hydrogen group. It has the process of removing this solvent after carrying out the reaction of bridge | crosslinking and / or extension | extension reaction, and carrying out reaction.

  The organic solvent is not particularly limited as long as the solvent can dissolve and / or disperse the toner material. What the boiling point of this organic solvent is less than 150 degreeC is preferable at the point which volatilization removal of an organic solvent is easy. Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, Acetone, tetrahydrofuran and the like can be used alone or in combination of two or more. The amount of the solvent used is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts with respect to 100 parts of the toner composition.

  The aqueous medium used in the present invention is used by adding polyurethane resin fine particles in advance. The polyurethane-based resin can be obtained by reacting a crystalline polyester diol, a diisocyanate, and a diol having a carboxyl group and then neutralizing. At this time, the volume average particle diameter of the polyurethane-based resin fine particles is preferably 50 to 400 nm. When the particle diameter of the resin fine particles is 400 nm or more, the amount of polyurethane-based resin fine particles necessary for coating the surface of the base particles increases, which may hinder the low-temperature fixability of the toner. If it is 50 nm or less, it may be difficult to uniformly coat the toner base particles.

  The water used for the aqueous medium may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The base particles are formed by reacting a compound having an active hydrogen group with a dispersion made of a polymer having a group capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent in an aqueous medium. Is obtained. As a method for stably emulsifying or dispersing a polymer having a group capable of reacting with an active hydrogen group in an aqueous medium, a polymer having a group capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent (B ) Is added to the aqueous medium and dispersed by shearing force. A polymer having a group capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent and other toner materials such as a colorant, a release agent, a charge control agent, and a resin are emulsified or dispersed in an aqueous medium. However, it is more preferable that the toner material is mixed in advance and dissolved or dispersed in an organic solvent, and then the mixture is added to an aqueous medium and dispersed. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent are not necessarily mixed when forming the base particles in an aqueous medium. It may be added after. For example, a colorant can be added by a known dyeing method after forming base particles that do not contain a colorant.

  A method for emulsifying or dispersing a polymer having a group capable of reacting with an active hydrogen group in an aqueous medium is not particularly limited, but is a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, an ultrasonic wave. Known equipment such as can be applied. In order to make the particle size of the dispersion 2 μm to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 5000 rpm to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 minutes to 5 minutes. The temperature at the time of dispersion is usually 0 ° C. to 150 ° C. (under pressure), preferably 40 ° C. to 98 ° C. When the temperature is within the above range, it is preferable to disperse at a high temperature from the viewpoint that the dispersion composed of a polymer having a group capable of reacting with an active hydrogen group has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used is usually 50 parts by mass to 2000 parts by mass, and preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the toner material containing a polymer having a group capable of reacting with an active hydrogen group. If the amount is less than 50 parts by mass, the dispersion state of the toner material is poor, and base particles having a predetermined particle size cannot be obtained. If it exceeds 2000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohols as dispersants for emulsifying and dispersing the dispersion in which the toner material is dispersed in an aqueous medium Amine salt types such as fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride Types of cationic surfactants, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine and N-alkyl-N, - amphoteric surfactants, such as dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Examples of the product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Limited). , Unidyne DS-101, DS-102 (manufactured by Taikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Chemical Co., Ltd.) Company-made), Xtop EF-102, 103, 104, 105, 11 , 123A, 123B, 306A, 501,201,204, (Ltd. Tochem Products), Ftergent F-100, F150 (manufactured by KK Neos), and the like.

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Limited), Unidyne DS-202 (Daikin Industries) Manufactured by Daikin Ink Chemical Co., Ltd., Xtop EF-132 (manufactured by Tochem Products Co., Ltd.), and footent F-300 (manufactured by Neos Co., Ltd.) Etc.

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  In the case where an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. In addition, it can be removed by an operation such as enzymatic degradation.

  When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the structure of the group capable of reacting with the active hydrogen group possessed by the polymer having a group capable of reacting with the active hydrogen group and the reactivity of the compound having the active hydrogen group. Is usually 10 minutes to 40 hours, preferably 2 hours to 24 hours. The reaction temperature is generally 0 ° C to 150 ° C, preferably 40 ° C to 98 ° C. Moreover, a well-known catalyst can be used as needed.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, a method of spraying the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles and evaporating and removing the aqueous dispersant together is also possible. The dry atmosphere in which the emulsified dispersion is sprayed is a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., and is heated to a temperature higher than the boiling point of the solvent having the highest boiling point among the solvents used. Various airflows are commonly used. By using a spray dryer, belt dryer, rotary kiln or the like, the desired quality can be obtained in a short time.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.

  In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Although the powder obtained after drying may be classified, it is preferable in terms of efficiency to perform classification in a liquid. The unnecessary fine particles or coarse particles after the classification operation can be returned to the kneading step and used as a raw material for the particles. At that time, fine particles or coarse particles may be in a wet state.

The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
(Toner acid value)
Controlling the acid value of the toner of the present invention is effective for the fixing characteristics (low temperature fixability, high temperature offset resistance). The acid value of the toner of the present invention is preferably 10 mgKOH / g to 30 mgKOH / g. When the acid value of the toner exceeds 30 mgKOH / g, the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high temperature offset resistance is affected. On the other hand, when the acid value of the toner is less than 10 mgKOH / g, the extension or crosslinking reaction of the modified polyester tends to proceed, and the minimum fixing temperature becomes high.
(Toner glass transition point)
The glass transition point of the toner of the present invention is preferably 40 ° C. to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. If the glass transition point is less than 40 ° C., blocking in the developing machine and filming on the photoreceptor are likely to occur, and if it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.
(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 part by weight of toner to 100 parts by weight of carrier. 10 parts by mass is preferred. Conventionally known magnetic carriers such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 μm to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Such as fluoro terpolymers such as terpolymer of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
[Example 1]
-Preparation of resin fine particle dispersion-
In a reaction vessel equipped with a stirring bar and a thermometer, 160 parts of dehydrated ethyl acetate, 130 parts of crystalline polyester diol (SE 2606, hydroxyl value 43 mgKOH / g, weight average molecular weight 2600, melting point 65 ° C., manufactured by Ito Oil Co., Ltd.), dimethylol 13 parts of propionic acid was added and stirred at 400 rpm for 60 minutes in the system temperature in a nitrogen stream to obtain a uniform solution. Further, 17 parts of 1,6-hexamethylene diisocyanate and 3 parts of triethylamine as a molecular weight modifier were added and reacted for 8 hours. After confirming disappearance of the absorption peak of the isocyanate group by IR measurement, the system temperature was lowered to 50 ° C. Thereafter, 10 parts of triethylamine was added for neutralization to obtain a polyurethane resin. Furthermore, 350 parts of distilled water heated to 50 ° C. was added and stirred vigorously to obtain a polyurethane resin fine particle dispersion. The dispersion was subjected to air bubbling for 2 hours, and ethyl acetate in the system was distilled off to obtain [Polyurethane resin fine particle dispersion 1]. The acid value of the polyurethane-based resin before neutralization was 35 mgKOH / g. Moreover, the volume average particle diameter measured by the laser type particle size distribution measuring apparatus (LA-920, manufactured by HORIBA, Ltd.) of the polyurethane resin fine particles was 62 nm, and the solid content was 33%. The melting point of the dried resin was 70 ° C.
-Preparation of aqueous medium-
1023 parts of water, 50 parts of [polyurethane resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. This was designated as [Aqueous medium 1].
-Synthesis of unmodified polyester-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added and reacted at 230 ° C. for 8 hours at normal pressure. Furthermore, after reacting at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Unmodified Polyester 1]. [Non-modified Polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 25 mgKOH / g.
-Synthesis of polyesters having hydroxyl groups-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours at normal pressure. Furthermore, it was made to react at the reduced pressure of 10 mmHg-15 mmHg for 5 hours, and [Polyester 1 which has a hydroxyl group] was obtained. [Polyester 1 having a hydroxyl group] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

Next, 410 parts of [Polyester 1 having a hydroxyl group], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.
-Synthesis of ketimine-
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.
-Synthesis of master batch-
1200 parts of water, 540 parts of carbon black (Printex35, manufactured by Degussa AG), [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], 1200 parts of unmodified polyester resin were added, and Henschel mixer (former Mitsui Mining Co., Ltd. ( Manufactured by the current Nippon Coke Kogyo Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].
-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 378 parts of [Unmodified Polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84, manufactured by Orient Chemical Co., Ltd.), 947 parts of ethyl acetate are charged. The temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Thereafter, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed a liquid at a rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and a volume of 0.5 mm zirconia beads of 80 volumes. Dispersion of carbon black and WAX was performed under the conditions of% filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [Non-modified Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.
-Emulsification-> Solvent removal-
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and rotated using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.) Mixing was performed at several 5000 rpm for 1 minute. Thereafter, 1200 parts of [Aqueous medium 1] was added to the container, and mixed for 20 minutes at 13,000 rpm using a TK homomixer to obtain [Emulsified slurry 1].

  [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.86 μm and a number average particle size of 5.11 μm (measured with Multisizer II).

−Washing → Drying−
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
[1]: 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
[2]: 100 parts of distilled water was added to the filter cake of [1], mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
[3]: 100 parts of 10% hydrochloric acid was added to the filter cake of [2], mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
[4]: Add 300 parts of ion-exchanged water to the filter cake of [3], mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter twice to obtain [filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved base particles were obtained with an opening of 75 μm mesh.

To 100 parts of the obtained base particles, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer to obtain [Toner 1].
[Example 2]
In [Example 1], [Toner 2] was used in the same manner as Example 1 except that the following [Polyurethane resin fine particle dispersion 2] was used instead of [Polyurethane resin fine particle dispersion 1]. ] Was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 300 parts of dehydrated ethyl acetate, 230 g of crystalline polyester diol (SE2606, manufactured by Ito Oil Co., Ltd.) and 11 parts of dimethylolpropionic acid, and the system temperature was 400 rpm. The mixture was stirred at 60 ° C. for 30 minutes in a nitrogen stream to obtain a uniform solution. Further, 28 parts of 1,6-hexamethylene diisocyanate and 5.5 parts of triethylamine were added and reacted for 8 hours. After confirming disappearance of the absorption peak of the isocyanate group by IR measurement, the system temperature was lowered to 50 ° C., and neutralized by adding 9 g of triethylamine to obtain a polyurethane resin. Thereafter, 607 g of distilled water heated to 50 ° C. was added and stirred vigorously to obtain a polyurethane resin fine particle dispersion. Further, air bubbling was performed on this dispersion for 2 hours to distill off ethyl acetate in the system, thereby obtaining [Polyurethane resin fine particle dispersion 2]. The acid value of the polyurethane-based resin before neutralization was 16 mgKOH / g. Moreover, the volume average particle diameter measured by the laser type particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.) of the polyurethane resin fine particles was 95 nm, and the solid content was 33%. The melting point of the dried resin was 71 ° C.
Example 3
In [Example 1], [Toner 3] was used in the same manner as in Example 1 except that the following [Polyurethane resin fine particle dispersion 3] was used instead of [Polyurethane resin fine particle dispersion 1]. ] Was obtained.
-Synthesis of crystalline polyester diol-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 100 parts of 1,4-butanedioic acid, 100 parts of 1,6-hexanediol and 2 parts of dibutyltin oxide were placed at 230 ° C. at normal pressure. For 8 hours, and further reacted for 5 hours at a reduced pressure of 10 mmHg to 15 mmHg to obtain [Crystalline Polyester Diol 2]. [Crystalline polyester diol 2] had a number average molecular weight of 2800, a weight average molecular weight of 7000, and a melting point of 89 ° C.
-Preparation of polyurethane resin fine particle dispersion-
A reaction vessel equipped with a stir bar and a thermometer was charged with 550 parts of dehydrated ethyl acetate, 450 parts of [crystalline polyester diol 2], and 20 parts of dimethylolpropionic acid, and the system temperature was 60 ° C. at 400 rpm and nitrogen. The mixture was stirred for 30 minutes in an air stream to obtain a uniform solution. Further, 50 parts of 1,6-hexamethylene diisocyanate and 9 parts of triethylamine were added and reacted for 8 hours. After confirming disappearance of the absorption peak of the isocyanate group by IR measurement, the system temperature was lowered to 50 ° C., and neutralized by adding 12 parts of triethylamine to obtain a polyurethane resin. Thereafter, 1055 parts of distilled water heated to 50 ° C. was added and stirred vigorously to obtain a polyurethane resin fine particle dispersion. Further, this dispersion was subjected to air bubbling for 2 hours, and ethyl acetate in the system was distilled off to obtain [Polyurethane resin fine particle dispersion 3]. The acid value of the polyurethane-based resin before neutralization was 15 mg KOH / g, the volume average particle size measured with a laser particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.) was 86 nm, and the solid content was 33%. . The dried resin had a melting point of 91 ° C.
Example 4
[Toner 4] was obtained in the same manner as in Example 1, except that the following [Unmodified Polyester 2] was used instead of [Unmodified Polyester 1].
-Synthesis of unmodified polyester-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 248 parts of terephthalic acid, 6 parts of adipic acid and dibutyl 2 parts of tin oxide was added and reacted at 230 ° C. for 8 hours at normal pressure. Then, after reacting for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Unmodified Polyester 2]. [Non-modified Polyester 2] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 67 ° C., and an acid value of 25 mgKOH / g.
Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that the following [Unmodified Polyester 3] was used instead of [Unmodified Polyester 1].
-Synthesis of unmodified polyester-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added and reacted at 230 ° C. for 8 hours at normal pressure. Thereafter, the reaction was further performed at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours, and then 48 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Unmodified Polyester 3]. [Non-modified Polyester 3] had a number average molecular weight of 2,300, a weight average molecular weight of 6,800, a Tg of 45 ° C., and an acid value of 29 mgKOH / g.
Example 6
[Toner 6] was obtained in the same manner as in Example 1 except that the following [Aqueous medium 2] was used instead of [Aqueous medium 1] in Example 1.
-Adjustment of aqueous media-
1023 parts of water, 50 parts of [polyurethane resin fine particle dispersion 1], 30 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. This is designated as [Aqueous medium 2].
[Comparative Example 1]
[Toner 7] was obtained in the same manner as in Example 1, except that the following [Vinyl resin fine particle dispersion 1] was used instead of [Polyurethane resin fine particle dispersion 1].

-Preparation of vinyl resin fine particle dispersion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 83 parts of styrene, 83 parts of methacrylic acid Parts, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The obtained emulsion was heated to a system temperature of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [vinyl resin fine particle dispersion 1] was obtained. The volume average particle size of [Vinyl resin fine particle dispersion 1] measured with a laser particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) was 105 nm. A portion of [Fine Particle Dispersion 4] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

Table 1 shows the physical property values of the obtained toner.
(Development of developer)
A developer comprising 5% by weight of toner and 95% by weight of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin was prepared.
(Developer evaluation)
Using Rigoh Co., Ltd. image Neo Neo 450 capable of printing 45 sheets of A4 size paper per minute, continuous printing was performed and the following criteria were evaluated. The evaluation results are shown in Table 1.

（評価項目）
（ａ）粒径
トナーの粒径は、コールターエレクトロニクス社製の粒度測定器「コールターカウンターＴＡＩＩ」を用い、アパーチャー径１００μｍで測定した。体積平均粒径および個数平均粒径についても前記粒度測定器により求めた。
（ｂ）定着性
株式会社リコー製ｉｍａｇｉｏ Ｎｅｏ ４５０を用いて、普通紙及び厚紙の転写紙（株式会社リコー製 タイプ６２００及びＮＢＳリコー製複写印刷用紙＜１３５＞）にベタ画像で、１．０±０．１ｍｇ／ｃｍ２のトナーが現像される様に調整を行った。さらに、定着ベルトの温度が可変となる様に調整を行い、普通紙でオフセットが発生しない上限温度を測定し、厚紙で定着下限温度を測定した。本発明における定着下限温度は、得られた定着画像をパットで擦った後の画像濃度の残存率が７０％以上となる定着ロール温度を指す。
（ｃ）耐熱保存性
トナーを５０℃×８時間保管後、４２メッシュのふるいにて２分間ふるい、金網上の残存率をもって耐熱保存性とした。耐熱保存性の良好なトナーほど残存率は小さい。以下の４段階で評価した。
×： ３０％以上
△： ２０〜３０％
○： １０〜２０％
◎： １０％未満
（ｄ）酸価
本発明における酸価（ＡＶ）、水酸基価（ＯＨＶ）は、次のような手順で決定される。
測定装置： 電位差自動滴定装置 ＤＬ−５３ Ｔｉｔｒａｔｏｒ（メトラー・トレド株式会社製）
使用電極： ＤＧ１１３−ＳＣ（メトラー・トレド株式会社製）
解析ソフト： ＬａｂＸ Ｌｉｇｈｔ Ｖｅｒｓｉｏｎ １．００．０００
装置の校正： トルエン１２０ｍＬとエタノール３０ｍＬの混合溶媒を使用。
測定温度： ２３℃
測定条件は以下のとおりである。
Ｓｔｉｒ
Ｓｐｅｅｄ ［％］ ２５
Ｔｉｍｅ ［ｓ］ １５
ＥＱＰ ｔｉｔｒａｔｉｏｎ
Ｔｉｔｒａｎｔ／Ｓｅｎｓｏｒ
Ｔｉｔｒａｎｔ ＣＨ_３ＯＮａ
Ｃｏｎｃｅｎｔｒａｔｉｏｎ［ｍｏｌ／Ｌ］ ０．１
Ｓｅｎｓｏｒ ＤＧ１１５
Ｕｎｉｔ ｏｆ ｍｅａｓｕｒｅｍｅｎｔ ｍＶ
Ｐｒｅｄｉｓｐｅｎｓｉｎｇ ｔｏ ｖｏｌｕｍｅ
Ｖｏｌｕｍｅ ［ｍＬ］ １．０
Ｗａｉｔ ｔｉｍｅ ［ｓ］ ０
Ｔｉｔｒａｎｔ ａｄｄｉｔｉｏｎ Ｄｙｎａｍｉｃ
ｄＥ（ｓｅｔ） ［ｍＶ］ ８．０
ｄＶ（ｍｉｎ） ［ｍＬ］ ０．０３
ｄＶ（ｍａｘ） ［ｍＬ］ ０．５
Ｍｅａｓｕｒｅ ｍｏｄｅ Ｅｑｕｉｌｉｂｒｉｕｍ ｃｏｎｔｒｏｌｌｅｄ
ｄＥ ［ｍＶ］ ０．５
ｄｔ ［ｓ］ １．０
ｔ（ｍｉｎ） ［ｓ］ ２．０
ｔ（ｍａｘ） ［ｓ］ ２０．０
Ｒｅｃｏｇｎｉｔｉｏｎ
Ｔｈｒｅｓｈｏｌｄ １００．０
Ｓｔｅｅｐｅｓｔ ｊｕｍｐ ｏｎｌｙ Ｎｏ
Ｒａｎｇｅ Ｎｏ
Ｔｅｎｄｅｎｃｙ Ｎｏｎｅ
Ｔｅｒｍｉｎａｔｉｏｎ
ａｔ ｍａｘｉｍｕｍ ｖｏｌｕｍｅ ［ｍＬ］ １０．０
ａｔ ｐｏｔｅｎｔｉａｌ Ｎｏ
ａｔ ｓｌｏｐｅ Ｎｏ
ａｆｔｅｒ ｎｕｍｂｅｒ ＥＱＰｓ Ｙｅｓ
ｎ＝ １
ｃｏｍｂ． ｔｅｒｍｉｎａｔｉｏｎ ｃｏｎｄｉｔｉｏｎｓ Ｎｏ
Ｅｖａｌｕａｔｉｏｎ
Ｐｒｏｃｅｄｕｒｅ Ｓｔａｎｄａｒｄ
Ｐｏｔｅｎｔｉａｌ １ Ｎｏ
Ｐｏｔｅｎｔｉａｌ ２ Ｎｏ
Ｓｔｏｐ ｆｏｒ ｒｅｅｖａｌｕａｔｉｏｎ Ｎｏ
（酸価の測定方法）
ＪＩＳ Ｋ００７０−１９９２に記載の測定方法（中和滴定法）に準拠して下記の方法で求めた。

(Evaluation item)
(A) Particle Size The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle size and number average particle size were also determined by the particle size measuring instrument.
(B) Fixability A solid image and a transfer sheet of plain paper and cardboard (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) with a solid image of 1.0 ± Adjustment was performed so that 0.1 mg / cm 2 of toner was developed. Further, adjustment was made so that the temperature of the fixing belt was variable, the upper limit temperature at which no offset was generated on plain paper was measured, and the lower limit fixing temperature was measured on thick paper. The minimum fixing temperature in the present invention refers to a fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad is 70% or more.
(C) Heat-resistant storage stability After storing the toner at 50 ° C. for 8 hours, the toner was sieved with a 42-mesh sieve for 2 minutes, and the residual rate on the wire mesh was defined as heat-resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
×: 30% or more Δ: 20-30%
○: 10 to 20%
A: Less than 10% (d) Acid value The acid value (AV) and hydroxyl value (OHV) in the present invention are determined by the following procedure.
Measuring apparatus: potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of apparatus: Use a mixed solvent of 120 mL of toluene and 30 mL of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potentialial 2 No
Stop for revaluation No
(Measurement method of acid value)
It calculated | required with the following method based on the measuring method (neutralization titration method) of JISK0070-1992.

    Sample preparation: 0.5 g of sample is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.

The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)
(E) Tg measuring method The measuring method of Tg is outlined. As an apparatus for measuring Tg, TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.

About 10 mg of sample is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Heat from room temperature to 150 ° C. at a heating rate of 10 ° C./min and hold at 150 ° C. for 10 minutes. Thereafter, the sample was cooled to room temperature and allowed to stand for 10 minutes, and re-heated to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere to perform DSC measurement. Tg was calculated from the contact point between the tangent and the base line at the inflection point in the vicinity of Tg of the endothermic curve, using the analysis system in the TAS-100 system.
(F) Image density After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite Co., Ltd.). The density was selected and measured at random at 5 points for each color, and the average for each color was determined.
(Evaluation was performed by continuously running an image chart of 5% image area up to 100,000 sheets.)
(G) Molecular weight The molecular weight of the resin was measured under the following conditions using GPC (gel permeation chromatography).

Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL injection of 0.05 to 0.6 wt% sample Using molecular weight calibration curve created from monodisperse polystyrene standard sample from resin molecular weight distribution measured under the above conditions The weight average molecular weight of the toner was calculated. In addition, when measuring the molecular weight of the prepolymer having an isocyanate group, a sample in which the isocyanate group was sealed was prepared by adding 3-fold equivalent of dibutylamine to the isocyanate group, and used for GPC measurement. .

JP 11-249339 A

Claims (7)

In an organic solvent, a compound having an active hydrogen group, a polymer having a reactive group capable of an active hydrogen group, a colorant, Ru obtain a first liquid to a material comprising a release agent dissolved or dispersed step ,
The first liquid, the resulting Ru step the second liquid is emulsified or dispersed in an aqueous medium containing fine particles of polyurethane resin,
Has from the second liquid as engineering to remove the organic solvent,
The polyurethane-based resin is a toner production method obtained by reacting a crystalline polyester diol, a diisocyanate, and a diol having a carboxyl group, and then neutralizing. Particles of the polyurethane resin is a volume average particle diameter of 50 to 400 nm, method for producing a toner according to claim 1. The polyurethane-based resin before being neutralized, acid value of 15~40mgKOH / g, method for producing a toner according to claim 1 or 2. The polyester diol, melting point of 65 to 100 ° C., method for producing a toner according to any one of claims 1 to 3.   A toner manufactured by the toner manufacturing method according to claim 1. Containing toner according to claim 5, developer.   Means for forming an electrical latent image on the photoreceptor;
  An image forming apparatus having means for developing the electrical latent image formed on the photoreceptor with the developer according to claim 6.