Magenta toner

0001The present disclosure provides an improved phase inversion emulsification (PIE) process for producing resin emulsions useful in the production of magenta toners, and more specifically, more rapid and effective solvent removal in the latex distillation step of PIE. It relates to an improved method for producing a commercial amount of toner, starting with an improved solvent stripping process that results. The use of the accelerated process disclosed herein increases the efficiency of latex production, reduces the cost of latex production, and results in more efficient toner production.

0002The latex emulsion of the resin is produced using a solvent reusing PIE process that dissolves the resin in a mixture of water and an organic solvent (eg, methyl ethyl ketone (MEK), isopropyl alcohol (IPA), or both) and is uniform water in oil. (W / O) dispersions (ie, water droplets dispersed in a continuous oil matrix) may be created. Water is then added to convert the dispersion into a stable oil-in-water (O / W) latex (water as a continuous phase).

0003The organic solvent may be removed (generally by vacuum distillation) and surfactants and / or other reagents (eg, preservatives) may be added to give a stable latex with a relatively high solid content of the resin. .. Such latex may be used for many purposes, including in emulsification agglutination (EA) methods for producing toner particles (eg, US Pat. Nos. 5,853,943, 5,902,710; 5,910,387; 5,916,725. See Nos. 5,919,595; Nos. 5,925,488, 5,977,210 and 5,994,020, and US Patent Publication No. 2008/0107989).

0004The production efficiency of magenta toner can be low, with, for example, low yields, low throughput, high GSD values (eg, resulting from large amounts of fine particles and / or coarse particles). Fluctuations may occur due to interference with red colorants and other toner components.

0005It would be beneficial to develop processes that improve latex production and magenta toner production.

<p num="0006"> The present disclosure describes an improved process for producing a commercial amount of magenta toner using an improved process for producing a latex emulsion. The product latex particles are produced much faster than the latex particles produced by conventional methods and are suitable for use in toner compositions, especially magenta toners. The distillation step of the PIE of interest occurs at a higher temperature, eg, above the Tg of the resin, or above the boiling point of the solvent, facilitating solvent removal and altering the surface of the latex particles.</p>

<p num="0007"> In some embodiments (a) Latex is produced by phase inversion emulsification (PIE) of a first emulsion containing a first resin and solvent, at a temperature higher than the Tg of the amorphous resin, higher than the melting point of the crystalline resin, or the first. When contained in an emulsion, the first emulsion exposed to both temperatures is used to distill the solvent; (b) Combining latex with wax and magenta colorants to form a second emulsion; (c) Adding a flocculant to the second emulsion to create agglomerated particles; (d) including fusing the agglomerated particles to produce the magenta toner. The magenta toner is similarly made, comprising said control resin made at a temperature lower than Tg of an amorphous resin, a temperature lower than the melting point of a crystalline resin, or a solvent distillation temperature of both when contained in the control resin. Disclosed are methods of producing magenta toner in commercial quantities, produced in high yields, high throughput, in short time, or in combination thereof, when compared to control magenta toner.</p>

0008In the process of interest, the polyester resin is dissolved in a solvent and the solvent may be a solvent mixture such as methyl ethyl ketone (MEK) and isopropanol (IPA), distilled water (DIW) and optionally a base such as ammonia. A small amount of base may be used to partially neutralize the polyester and promote dispersion of the resin in the solvent and DIW. A second amount of base (eg, ammonia) may be added to the resin solution to neutralize additional acid end groups on the polyester chain, followed by a second amount of DIW and water continuity by phase inversion. A uniform suspension of polyester particles may be made in the phase. The emulsion is then exposed to high temperatures to facilitate solvent removal and scrape the particle surface to a state where agglomeration is likely to occur.

0009In the EA process, the rate of particle agglomeration affects the overall EA cycle time, which determines the productivity of the EA toner. The agglutination process is affected by the rate of agglutination of the latex particles, as latex constitutes the highest amount of raw material in the batch. Thus, for example, the productivity of the EA toner can be increased by increasing the rate of aggregation of the latex particles by modifying the latex particles (eg, their morphology and other properties, eg, the surface structure of the particles).

0010The agglutination rate depends, in part, on the probability of collision between particles, the probability of binding during collision and the subsequent desorption of particles from the agglomerates. The collision probability can vary depending on (i) Brownian motion determined by the temperature of the system, and (ii) the fluid flow motion determined by the viscosity of the fluid medium and external agitation. The probability of adhesion and detachment may vary depending on the type of physicochemical interaction between the particles and, to some extent, the velocity gradient in the medium. Therefore, in order to promote particle agglomeration, the collision probability and the particle binding probability should be increased, and the particle detachment probability should be decreased.

0011According to the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the overall interaction between particles that affects the rate of aggregation is the superposition of van der Waals forces and the interaction of the electrostatic double layer. Therefore, measures to increase the agglutination rate are to reduce or, for that matter, eliminate van der Waals forces and electrostatic double layer interactions between latex particles.

0012The literature reports the existence of a "hairy" layer around latex particles that can create a three-dimensional barrier to aggregation (Verdegan &amp; Anderson, J Colloid Interf Sci, 158, 372-381, 1993; Chow &amp; Takamura, J Colloid Interf Sci, 125, 226-236, 1988; and Midmore &amp; Hunter, J Colloid Interf Sci, 122, 521-529, 1988).

0013Heat treatment can reduce, or even eliminate, the hair layer (Seebergh &amp; Berg, Colloids Surf A, 100, 139, 1995; Rosen &amp; Saville, J Colloid Interf Sci, 140, 82, 1990; And Rosen &amp; Saville, J Colloid Interf Sci, 149, 542, 1992), establishing good agreement between theoretical DLVO models and experimental results.

0014Resin polymer chains may extend from the particle surface, creating "hairy portions" on the particle surface. The trichomes on the latex particles extend towards the massive solution due to electrostatic repulsion between the ionic groups neutralized by ammonia during the latex conversion process. As the temperature rises above Tg, some of the hairy layers will collapse and return to the particle surface. This reduces electrostatic repulsion. This may also partially remove the steric barrier, providing a more exposed particle surface for enhanced agglomeration between the particles, which may improve toner productivity.

0015Unless otherwise indicated, it should be understood that all numbers used herein and in the claims to describe quantities, conditions, etc. have been amended by the term "about" in all cases. "About" means to show a variation of less than 10% of the stated value. In addition, as used herein, the terms "equivalent," "similar," "essentially," "substantially," "approximately," "fit with," or these grammatical variants , Has a generally accepted definition, or is understood to have at least the same meaning as "about."

0016As used herein, "commercial" refers to toner production scales that are larger than bench scales and larger than pilot scales. In terms of dry toner, commercial scale dry toner is more than about 100 kg, more than about 200 kg, more than about 300 kg, more than about 400 kg, more than about 500 kg in a single implementation. , More than about 600 kg, more than about 700 kg, more than about 800 kg, more than about 900 kg, more than about 1000 kg, more than about 1250 kg, more than about 1500 kg, more than about 1750 kg, about Manufactured in more than 2000 kg, more than about 2250 kg, more than about 2500 kg, more than about 2750 kg, more than about 3000 kg, more than about 3250 kg, more than about 3500 kg, or more .. In terms of batch reaction, commercial production, in size and quantity, is at least about 1000 gal, at least about 1250 gal, at least about 1500 gal, at least about 1750 gal, at least about 2000 gal, at least about 2250 gal, at least about 2500 gal, at least about 2750 gal, Perform with a reactor of at least about 3000 gal or more.

0017Any resin may be used when preparing the latex emulsion of the present disclosure. The resin may be an amorphous resin, a crystalline resin, and / or a combination thereof. The resin may be a polyester resin, including, for example, the resins described in US Pat. No. 6,593,049 and US Pat. No. 6,756,176. Suitable resins may also include mixtures of amorphous polyester resins and crystalline polyester resins as described in US Pat. No. 6,830,860. Suitable resins may include mixtures of high molecular weight amorphous polyester resins and low molecular weight amorphous polyester resins.

0018The resin may be a polyester resin made by reacting a diol with a diacid in the presence of a catalyst of an arbitrary element.

0019The diol may be selected, for example, in an amount of about 40 to about 60 mol%, about 42 to about 55 mol%, about 45 to about 53 mol% of the resin, and optionally the second diol. , About 0 to about 10 mol% of the resin, may be selected to be in an amount of about 1 to about 4 mol%. The diacid may be selected, for example, in an amount of about 40 to about 60 mol%, about 42 to about 52 mol%, about 45 to about 50 mol% of the resin, and optionally a second second. The acid may be selected to be in an amount of about 0 to about 10 mol% of the resin.

0020When preparing either crystalline polyester or amorphous polyester, a polycondensation catalyst may be used, and the polycondensation catalyst includes tetraalkyl titanate, dialkyltin oxide (for example, dibutyltin oxide), tetraalkyltin (for example, dibutyltin oxide). For example, dibutyltin dilaurate), dialkyltin oxide hydroxide (eg, butyltin oxide hydroxide), aluminum alkoxide, alkylzinc, dialkylzinc, zinc oxide, stannous oxide, or a combination thereof. Such catalysts may be utilized in an amount of, for example, from about 0.01 mol% to about 5 mol%, based on the starting material diacid or diester used to make the polyester resin.

0021Examples of crystalline resins include polyester, polyamide, polyimide, polyolefin, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, mixtures thereof and the like. Specific crystalline resins are polyester-based, for example, poly (ethylene-adipate), poly (propylene-adipate), poly (butylene-adipate), poly (pentylene-adipate), poly (hexylene-adipate), poly (poly). Octylene-adipate, poly (ethylene-succinate), poly (propylene-succinate), poly (butylene-succinate), poly (pentylene-succinate), poly (hexylene-succinate), poly (octylene-succinate), poly (ethylene) -Sevacate), Poly (Propene-Sevacate), Poly (Butylene-Sevacate), Poly (Pentylene-Sevacate), Poly (Hexylene-Sevacate), Poly (octylene-Sevacate), Poly (Decilene-Sevacate), Poly (Decilene- Decanoate), Poly (Ethylene-Decanoate), Poly (Ethylene Dodecanoate), Poly (Nonylene-Sevacate), Poly (Nonylene-Decanoate), Propene (Ethylene-Fumarate) -Copoly (Ethylene-Sevacate), Copoly (Ethylene-Ethylene- Fumarate)-Propene (Ethylene-decanoate), Copoly (Ethylene-Fumarate) -Copoli (Ethylene-Dodecanoate), Copoli (2,2-Dimethylpropan-1, It may be 3-diol-decanoate) -copoly (nonylene-decanoate), poly (octylene-adipate). Examples of polyamides are poly (ethylene-adipamide), poly (propylene-adipamide), poly (butylene-adipamide), poly (pentylene-adipamide), poly (hexylene-adipamide), poly (octylene-adipamide), poly (poly). Ethylene-succinimide) and poly (propylene-sebacamide). Examples of polyimides include poly (ethylene-adipimide), poly (propylene-adipimide), poly (butylene-adipimide), poly (pentylene-adipimide), poly (hexylene-adipimide), poly (octylene-adipimide), poly (poly (octylene-adipimide) Ethylene-succinimide), poly (propylene-succinimide) and poly (butylene-succinimide).

0022The crystalline resin may be present in an amount of, for example, about 1 to about 20% by weight of the toner component and about 2 to about 15% by weight of the toner component. The crystalline resin may have various melting points, for example, the melting points may be about 30 ° C to about 120 ° C and about 50 ° C to about 90 ° C. When measured by gel permeation chromatography (GPC), the crystalline resin may have a number average molecular weight (Mn) of, for example, about 1,000 to about 50,000, about 2,000 to about 25,000, and a weight average molecular weight (Mw). However, when determined by GPC, it may be, for example, about 2,000 to about 100,000 and about 3,000 to about 80,000. The molecular weight distribution (Mw / Mn) of the crystalline resin may be, for example, about 2 to about 6 and about 3 to about 5.

0023The amorphous resin or the combination of the amorphous resins used for the latex may have a glass transition temperature (Tg) of about 30 ° C to about 80 ° C and about 35 ° C to about 70 ° C. In some embodiments, the combined resin utilized in the latex has a melt viscosity at about 130 ° C of about 10 to about 1,000,000 Pa.^*S, about 50 ~ about 100,000 Pa^*S.

0024One type, two types, or more types of resins may be used. When two or more resins are used, the resins may be in any suitable ratio (eg, weight ratio), eg, about 1% (first resin) / 99% (second resin). ~ About 99% (first resin) / 1% (second resin), in some embodiments about 10% (first resin) / 90% (second resin) ~ about 90% ( 1st resin) / 10% (2nd resin) may be used.

0025Suitable toners of the present disclosure may include two types of amorphous polyester resins and one type of crystalline polyester resin. The weight ratio of these three types of resin is from about 30% of the first amorphous resin / 65% of the second amorphous resin / 5% of crystalline resin to about 60% of the first amorphous resin / 20%. It may be up to a second amorphous resin / 20% crystalline resin.

0026Suitable toners of the present disclosure may contain at least two types of amorphous polyester resins, high molecular weight resins and low molecular weight resins. As used herein, ultra-high molecular weight (HMW) amorphous resins may have a weight average molecular weight (Mw) of about 35,000 to about 150,000, about 45,000 to about 140,000, and low molecular weight (LMW) amorphous resins. , Mw may be about 10,000 to about 30,000 and about 15,000 to about 25,000.

0027The weight ratio of these two types of resin ranges from about 10% of the first amorphous resin / 90% of the second amorphous resin to about 90% of the first amorphous resin / 10% of the second amorphous resin. There may be.

0028The resin may have an acidic group and, in some embodiments, may be present at the polymer end. Examples of the acidic group include a carboxylic acidic group. The number of acidic groups may be controlled by adjusting the materials and reaction conditions used to make the resin.

0029The resin may have an acid value of about 2 mg to about 200 mg KOH / g number of resin, about 5 mg to about 50 mg, and about 10 mg to about 15 mg KOH / g number of resin.

0030Other suitable resins that can be used to make toner are styrene, acrylates such as alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, butyl isoacrylate, dodecyl acrylate, acrylic. Acid n-octyl, acrylic acid n-butyl, acrylic acid 2-Chloroethyl; β-carboxyethyl acrylate (β-CEA), phenylacrylate, methacrylate, butadiene, isoprene, acrylic acid, acrylonitrile, styrene acrylate, styrene butadiene, styrene methacrylate, etc., for example, methyl α-chloroacrylate, methacrylic Methyl acid acid, ethyl methacrylate, butyl methacrylate, butadiene, isoprene, metaacrylonitrile, acrylonitrile, vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, etc .; vinyl esters such as vinyl acetate, vinyl propionate, benzoate Vinyl acetate and vinyl butyrate; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc .; vinylidene halides, such as vinylidene chloride, vinylidene chlorofluoride, etc .; N-vinylindole, N-vinylpyrrolidone, methacrylate. , Acrylic acid, methacrylic acid, acrylamide, methacrylicamide, vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, vinylnaphthalene, p-chlorostyrene, vinyl chloride, vinyl bromide, vinyl fluoride, ethylene, propylene, butylene , Isobutylene and mixtures thereof. Mixtures of monomers may be used to make copolymers such as block copolymers, alternating copolymers, graft copolymers and the like.

0031In some embodiments, the shell latex, core latex, or both may be functionalized with a group that imparts hydrophobicity to the latex so as to improve its sensitivity to relative humidity. Suitable functional groups include, for example, alkaline earth resins or other metallic resins, including but not limited to calcium resinate, beryllium resinate, magnesium resinate, strontium resinate, barium resinate. , Radium resinate, zinc resinate, aluminum resinate, copper resinate, iron resinate, and combinations thereof. In some embodiments, the surface-functionalized latex may contain a calcium resinate as a functional group (see US Pat. No. 7,553,601).

0032For example, including alcohols, esters, ethers, ketones, amines, and combinations thereof, for example, about 30% by weight to about 400% by weight of resin, about 40% by weight to about 250% by weight of resin, and about 50% by weight of resin. The resin may be dissolved using any suitable organic solvent in an amount of% to about 100% by weight.

0033Suitable organic solvents (sometimes referred to as phase inversion agents) include, for example, methanol, ethanol, propanol, IPA, butanol, ethyl acetate, MEK, and combinations thereof. In some embodiments, the organic solvent may be immiscible with water and may have a boiling point of about 30 ° C to about 120 ° C to improve latex production after removal. , It may be selected to be lower, for example, lower than the Tg of the resin. In some embodiments, when at least two solvents are used, the solvent ratios are about 1: 2 to about 1:15, about 1: 2.5 to about 1: 12.5, about 1: 3 to about 1: 1. It may be 10, but other ratios may be used as design options.

0034Optionally, the resin may be mixed with a weak base, buffer or neutralizer. In some embodiments, a neutralizing agent may be used to neutralize the acidic groups of the resin, so that the neutralizing agent herein can be the source or content of the specification. That is sometimes called a "basic neutralizer". Any suitable basic neutralizing reagent may be used in accordance with the present disclosure. Suitable basic neutralizers may include inorganic basic agents and organic basic agents. Suitable basic agents include ammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, lithium hydroxide, potassium carbonate, and combinations thereof. Suitable basic agents include monocyclic and polycyclic compounds containing at least one nitrogen atom, such as secondary amines, such as aziridine, azetidine, piperazine, piperidine, pyridine, bipyridine, terpyridine, dihydropyridine. , Morpholine, N-alkylmorpholin, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicycloundecane, 1,8-diazabicycloundecene, dimethylated pentylamine, trimethylated pentylamine, pyrimidine , Pyrol, pyrrolidine, pyrrolidinone, indol, indoline, indanone, benzimidazole, imidazole, benzimidazole, imidazolone, imidazoline, oxazole, isooxazole, oxazoline, oxadiazol, thiazazole, carbazole, quinoline, isoquinoline, naphthylidine, triazine, triazole. , Tetrazole, pyrazole, pyrazoline, and combinations thereof. The monocyclic compound and the polycyclic compound may be unsubstituted or substituted at any carbon position on the ring.

0035The basic agent may be used in an amount of about 0.001% by weight to 50% by weight of the resin, about 0.01% by weight to about 25% by weight of the resin, and about 0.1% by weight to 5% by weight of the resin. The neutralizer may be added in the form of an aqueous solution. The neutralizer may be added in solid form. Multiple forms of base may be used in the process of interest. Therefore, the process may include a first base and use the second base in different or successive steps. The first base and the second base may be the same or different.

0036When the above-mentioned basic neutralizer is used in combination with a resin having an acidic group, a neutralization rate of about 25% to about 300% and about 50% to about 200% may be achieved. In some embodiments, the neutralization rate may be calculated by multiplying the molar ratio of basic groups given with the basic neutralizer to the acidic groups present in the resin by 100%. ..

0037The pH of the emulsion containing the resin having an acidic group may be raised to about 5 to about 12 and about 6 to about 11 by adding a basic neutralizing agent. Neutralization of acidic groups will improve emulsion formation.

0038Emulsions made in accordance with the present disclosure are the temperature at which the resin melts or softens, about 25 ° C to about 120 ° C, about 35 ° C to about 80 ° C, and the amount of water that the resin melts or softens. In that embodiment, deionized water (DIW) is included.

0039The process of the present disclosure may include adding a surfactant to the resin at high temperatures before or during the combination of reagents, for example in an emulsion, in a dispersion, and the like. A surfactant may be added before the resin is mixed at high temperature.

0040When a surfactant is utilized, the resin emulsion or dispersion may contain one, two or more surfactants. The surfactant may be selected from ionic surfactants and nonionic surfactants. Anionic and cationic surfactants are included in the term "ionic surfactants". In some embodiments, the surfactant may be added as a solid, or at a concentration of about 5% to about 100% by weight (pure surfactant), from about 10% to about 95% by weight. It may be added as a liquid at a concentration of%. In some embodiments, the surfactant may be utilized in an amount of about 0.01% to about 20% by weight, about 0.1% to about 16% by weight, and about 1% to about 14% by weight of the resin. ..

0041The process of the present invention contains at least one resin, at least one organic solvent, optionally a surfactant and optionally a neutralizer, by any known method, optionally at a temperature above room temperature (RT). Includes making a mixture and making a latex emulsion. The resins may be pre-blended before being combined or mixed.

0042In some embodiments, the high temperature for making the mixture is T of the resin._gNear or T_gtaller than. In some embodiments, the resin may be a mixture of low molecular weight amorphous resin and high molecular weight amorphous resin.

0043Therefore, the process of the present disclosure is a shortened process of contacting at least one resin with an organic solvent to prepare a resin mixture, heating the resin mixture to a high temperature, and stirring the mixture. In some cases, a neutralizing agent is added to neutralize the acidic group of the resin, water is added until phase inversion occurs to prepare a phase-inverted latex emulsion, and the latex is distilled at a high temperature to prepare a solvent. It may include removing, for example, producing a latex having a low polydispersity, a low proportion of fine particles, a low proportion of coarse particles, and a scraped particle surface.

0044In the phase inversion process, the resin may be dissolved in a low boiling organic solvent, which is in water when the concentration of the resin in the solvent is about 1% by weight to about 75% by weight and about 5% by weight to about 60% by weight. It is miscible or partially miscible. The resin mixture is then heated to temperatures from about 25 ° C to about 90 ° C and from about 30 ° C to about 85 ° C. The heating need not be maintained at a constant temperature, but may vary. For example, heating may be done slowly or stepwise until the desired temperature is reached.

0045Water is added, for example, in two portions and phase inversion to create a uniform aqueous dispersion of resin particles.

0046The organic solvent remains in both the resin particles and the aqueous phase at this stage. The organic solvent may then be distilled off, for example, by heating or vacuum distillation. The heating is chosen to be higher than the current procedure and higher than the Tg of the resin in the emulsion. The solvent may be selected to be ready for removal at such temperatures, i.e., a boiling point lower than the Tg of the resin, the same boiling point as the Tg of the resin, or of the resin so that it is ready to be removed from the emulsion. A solvent having a boiling point close to Tg may be selected.

0047In some embodiments, the resin to solvent ratio may be from about 8: 1 to about 3: 1. When two kinds of solvents are used and the LMW resin is contained, the ratio of the LMW resin, the first solvent and the second solvent may be, for example, about 10: 6: 1.5. When the HMW resin is contained together with two kinds of solvents, the ratio of the HMW resin, the first tree solvent and the second solvent may be, for example, about 10: 8: 2, but a different ratio. May be used.

0048The mixing temperature may be from about 35 ° C to about 100 ° C, from about 40 ° C to about 90 ° C, and from about 50 ° C to about 70 ° C.

0049Once the resin, optional element neutralizer and optional element surfactant have been combined, the mixture may then be contacted with the water of the first portion to form a W / O emulsion. Water may be added to make a latex with a solid content of about 5% to about 60% and about 10% to about 50%. Higher water temperatures may facilitate dissolution, but latex may be made at temperatures as low as room temperature. In some embodiments, the water temperature may be from about 40 ° C to about 110 ° C and from about 50 ° C to about 90 ° C.

0050The amount of water, including the water in the first portion, is an appropriate amount to make a W / O emulsion. Phase inversion can occur at a ratio of organic phase to aqueous phase of approximately 1: 1 (w / w or v / v). Thus, the first portion of water generally contains less than about 50% of the total volume or total weight of the final emulsion. The water in the first portion may be less than about 95%, less than about 90%, less than about 85%, or even less than the volume or weight of the organic phase. A smaller amount of water may be used in the first portion as long as a suitable W / O emulsion is produced.

0051When an alkaline aqueous solution or basic agent of any element, a surfactant of any element and water of the second part are added, a phase inversion occurs, and a dispersed phase containing droplets containing a molten component of the resin composition and a dispersed phase. A phase-inverted emulsion containing a continuous phase containing water is produced.

0052In some embodiments, mixing may be carried out using any means within the skill of one of ordinary skill in the art. For example, a glass kettle with an anchor blade impeller, an extruder, i.e. a twin screw extruder, a kneader, eg, a Haake mixer, a batch reactor, or a tightly mixed viscous material, a nearly uniform or uniform mixture. Mixtures may be made on any other device that can be created.

0053Stirring is not essential, but stirring may be used to promote latex formation. Any suitable stirring device may be utilized. In some embodiments, stirring may be carried out at speeds of about 10 rpm to about 5,000 rpm, about 20 rpm to about 2,000 rpm, and about 50 rpm to about 1,000 rpm. The agitation does not have to be constant and may vary. For example, the stirring speed may be increased as the heating of the mixture becomes uniform. In some embodiments, a homogenizer (ie, a high shear device) may be utilized to produce a phase-inverted emulsion. When used, the homogenizer may be operated at a speed of about 3,000 rpm to about 10,000 rpm.

0054The phase inversion point may change depending on the composition of the emulsion, heating temperature, stirring speed, etc., but the obtained resin is about 5% by mass to about 70% by mass, about 20% by mass to about 65% by mass, and about 30% by mass. Addition of optional element basic neutralizers, optional element surfactants and water to be present in an amount of% ~ about 60% by weight will result in phase inversion.

0055After the phase inversion, the phase inversion emulsion may be diluted by adding an additional optional surfactant, water and an alkaline aqueous solution of the optional element.

0056Distill at high temperature while stirring the emulsion to speed up solvent removal and scrape the particle surface. The high temperature is higher than Tg or higher than the melting point of the resin and is near the boiling point of the solvent. The resin emulsion particles may have an average diameter of less than about 300 nm, less than about 250 nm, and less than about 200 nm.

0057Heating may be performed, for example, by using a jacket and applying it to the outer surface of the container containing the emulsion. The temperature of the jacket is high, that is, higher than the Tg of the resin. The heating device heats the walls of the container and then passes through the emulsion contained in the container. Generally, the fluid layer adjacent to the inner surface of the vessel takes in the high temperature of the heating means because the contents of the vessel are under agitation. Heat is transferred to the central part of the emulsion by the action of mass, stirring of the emulsion, mechanical stirring, mixing, and the like. Since the solvent around it is first heated to a temperature close to, or higher than the boiling point of the solvent, these solvent molecules evaporate and the heat is transferred to the evaporated solvent. In this way, heat is transferred from the evaporated solvent to the gas phase, lowering the temperature of the emulsion. As a result, the overall batch temperature of the emulsion can be about 20 ° C lower than the high temperature applied. At the levels described herein, as a design option, depending on the resin used, the solvent used, etc., the temperature of the heating device can be adjusted to obtain the desired average of the overall emulsion temperature. it can.

0058Once sufficient solvent has been removed (determined by known analytical techniques such as gas chromatography (GC)), distillation is interrupted and latex is obtained. As is known in the art, liquids may be removed, particles may be washed, and the like. Resin particles are produced more rapidly and are suitable for use with toners and have a quality that facilitates and enhances toner production, especially on a commercial scale. The solvent stripping step is shortened due to the high temperature applied. The solvent stripping step is a similar process, but will be about 15% shorter, about 20% shorter, about 25% shorter, or even shorter than the solvent stripping step, which does not use high temperatures during the solvent removal step.

0059Desirable properties of the resin emulsion (ie, particle size and low residual solvent level) are achieved by adjusting the solvent, neutralizer concentration, treatment parameters (ie, reactor temperature, decompression and treatment time), etc. right.

0060As mentioned above, the resin mixture is brought into contact with water to form an emulsion, the solvent is removed from the mixture, and the resulting latex is used to make toner by any method within the skill of one of ordinary skill in the art. You may. In a suitable process, in some embodiments, by emulsification aggregation and fusion processes, the latex emulsion is combined with a magenta colorant (possibly in a dispersion), wax (sometimes in a dispersion) and other additives. The toner may be made into contact with each other.

0061One or more colorants may be added and various known suitable colorants such as dyes, pigments, dye mixtures, pigment mixtures, dye-pigment mixtures and the like may be included in the magenta toner. .. In some embodiments, when a colorant is present, the colorant is, for example, about 3 to about 15% by weight of the toner, about 4 to about 12% by weight of the toner, and about 5 to about 10% by weight of the toner. The amount may be included in the toner, but the amount of colorant may be outside these ranges.

0062Using any one or more colorants such as pigment red (PR) 122, PR185, PR192, PR202, PR206, PR235, PR269, or combinations thereof, such as PR122 and PR269 with a weight ratio of 1: 1. Magenta toner may be manufactured.

0063As a design option, the toner of interest may contain a colorant other than the red colorant in order to obtain the desired hue and / or shading.

0064Optionally, the wax may be combined with a resin and an optional colorant when creating the toner particles. The wax may be given as a wax dispersion and may contain one wax or a mixture of two or more different waxes.

0065When wax is included, the wax may be present, for example, in an amount of about 1% by weight to about 25% by weight of the toner particles and about 5% by weight to about 20% by weight of the toner particles, but the amount of wax. May be out of these ranges.

0066When a wax dispersion is used, the wax dispersion may contain any of the various waxes conventionally used in emulsified cohesive toner compositions. Selectable waxes include, for example, waxes having an average molecular weight of about 500 to about 20,000 and about 1,000 to about 10,000.

0067Usable waxes include, for example, polyolefins such as polyethylene containing linear polyethylene wax and branched polyethylene wax, polypropylene containing linear polypropylene wax and branched polypropylene wax, polyethylene / amide, polyethylene tetrafluoroethylene, and the like. Polyethylene tetrafluoroethylene / amide, naturally occurring waxes such as those obtained from plant or animal sources, and polypropylene waxes. In some embodiments, the wax mixtures and combinations described above may be used. In some embodiments, the wax may be crystalline or non-crystalline.

0068In some embodiments, the wax may be incorporated into the toner in the form of one or more aqueous emulsions or aqueous dispersions of the solid wax, for example, the particle size of the solid wax ranges from about 100 to about 500 nm. It may be.

0069The toner composition is prepared by an EA process, for example, an emulsion containing a colorant, a wax of any element, any other desirable or necessary additive, and the heat treated resin described herein. The containing mixture is optionally prepared by a process comprising aggregating in a surfactant as described herein and then fusing the agglomerated particles. A colorant, optionally a wax or other material (possibly in the form of a dispersion containing a surfactant), into an emulsion (which may be a mixture of two or more emulsions containing a resin). Mixtures may be prepared by addition. The pH of the resulting mixture may be adjusted with an acid such as acetic acid, nitric acid or the like. The pH of the mixture may be adjusted to about 2-5. In addition, in some embodiments, the mixture may be homogenized. When homogenizing the mixture, it may be mixed at, for example, about 600 to about 6000 ppm. Homogeneity may be achieved using any suitable means (eg, IKA ULTRA TURRAX T50 probe homogenizer).

0070After preparing the above mixture, a flocculant may be added to the mixture. Toners may be made using any suitable flocculant. Suitable flocculants include, for example, an aqueous solution of a divalent or multivalent cation material. The flocculant is, for example, an inorganic cationic flocculant, eg, aluminum polyhalogen, eg, polyaluminum chloride (PAC), or the corresponding bromide, fluoride or iodide, aluminum polysilicate, eg, polyaluminum sulfosilicate (. PASS) and water-soluble metal salts (aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxalate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate , Zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate), and combinations thereof. In some embodiments, a flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

0071The flocculant is used to make toner, for example, in an amount of about 0.1% to about 10% by weight, about 0.2% to about 8% by weight, and about 0.3% to about 5% by weight of the resin in the mixture. May be added to the mixture to be made.

0072The particles may be agglomerated until the desired desired particle size is obtained. For example, for average particle size, COULTER COUNTER may be used to monitor the particle size during the growth process. Thus, the mixture is kept at a high temperature, or slowly raised to, for example, a temperature of about 40 ° C to about 100 ° C, at which temperature the mixture is kept agitated for about 0.5 to about 6 hours, about. Aggregation may proceed by holding for 1 hour to about 5 hours to obtain aggregated particles. Once the desired particle size is reached, any element of shell resin may be added.

0073In some embodiments, the agglomerated particles may be coated with a resin coating to form a shell on the particle surface after the agglomeration is complete and prior to fusion. Thus, in some embodiments, the core may contain one or more of the amorphous and / or crystalline resins, as described herein. Any of the above resins, including heat treated resins, may be used in the shell.

0074A plurality of resins may be used in any suitable amount. Therefore, the first resin may be present in an amount of about 20% by weight to about 100% by weight and about 30% by weight to about 90% by weight of the entire shell resin. The second resin may be present in the shell resin in an amount of about 0% by weight to about 80% by weight and about 10% by weight to about 70% by weight of the shell resin.

0075The shell resin may be applied to the agglomerated particles by any method within the scope of the art. In some embodiments, the resin utilized to make the shell may be in the form of an emulsion containing any of the surfactants described above.

0076The shell may be formed on the agglomerated particles while heating to a temperature of about 30 ° C to about 80 ° C and about 35 ° C to about 70 ° C. The shell may be created for about 5 minutes to about 10 hours and about 10 minutes to about 5 hours.

0077The shell may be present in an amount of about 10% to about 40% by weight of the latex particles and about 20% to about 35% by weight of the latex particles.

0078Once the desired final particle size of the toner particles is reached, a base or buffer may be used to adjust the pH of the mixture to a value of about 3 to about 10 and about 5 to about 9. Adjusting the pH may be utilized to freeze (ie, stop) the growth of the toner particles. Examples of the base used to stop the growth of the toner include any suitable base, such as alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, etc.). Can be done. In some embodiments, a chelating agent (eg, ethylenediaminetetraacetic acid (EDTA)) may be added to facilitate the pH adjustment to the desired value.

0079The particles may be agglomerated to the desired particle size, coated with a shell of arbitrary elements, and then fused to the desired final shape, for example the fusion of the mixture from about 45 ° C to about 100 ° C. It may be done by heating to a temperature of about 55 ° C to about 99 ° C, which may be greater than or equal to Tg of the resin used to make the toner particles. Fusing may take about 0.01 to about 9 hours and about 0.1 to about 4 hours.

0080After agglomeration and / or fusion, the mixture may be cooled to RT (eg, about 20 ° C to about 25 ° C). If desired, it may be cooled quickly or slowly. A suitable cooling method may include introducing cold water into the jacket around the reactor. After cooling, the toner particles may optionally be washed with water and then dried. Drying may be carried out by any suitable drying method, including, for example, freeze-drying.

0081In some embodiments, the toner particles may also contain other additives of any element, if desired or required. For example, the toner may contain a positive charge control agent or a negative charge control agent in an amount of, for example, about 0.1 to about 10% by mass and about 1 to about 3% by mass of the toner. Examples of suitable charge control agents are quaternary ammonium compounds containing alkylpyridinium halides; hydrogen sulfate; alkylpyridinium compounds including those disclosed in US Pat. No. 4,298,672; disclosed in US Pat. No. 4,338,390. Compositions of Organic Sulfates and Organic Sulfates, Including Those; Cetylpyridinium Tetrafluoroborate; Distearyldimethylammonium Methyl Sulfate; Aluminum Salts, For example, BONTRON E84 or E88 (Orient Chemical Industries, Ltd.) ; A combination of these can be mentioned.

0082The toner particles may be blended with external additive particles containing a flow auxiliary additive after preparation, in which case the additive may be present on the surface of the toner particles. Examples of additives include metal oxides such as titanium oxide, silicon oxide, aluminum oxide, cerium oxide, tin oxide, mixtures thereof; colloidal silica and amorphous silica such as AEROSIL®, metal salts. And fatty acid metal salts (including zinc stearate and calcium stearate), or long chain alcohols such as UNILIN 700, and mixtures thereof. Each external additive may be present in an amount of about 0.1% to about 5% by weight of the toner and about 0.25% by weight to about 3% by weight of the toner, but the amount of the additive is in these ranges. It may be out of the range.

0083The toners of the present disclosure may be used as ultra-low melting point (ULM) toners containing suitable resins of suitable Tg, low melting point waxes and the like.

0084In some cases, the dry toner particles containing the shell may have the following characteristics, except for the external surface additive. (1) The volume mean diameter (also called "volume mean particle size") is, for example, about 3 to about 25 μm, about 4 to about 15 μm, about 5 to about 12 μm; (2) number mean geometric mean particle size distribution (GSDn) and / Or volume geometric mean particle size distribution (GSDv) is, for example, about 1.05 to about 1.55, about 1.1 to about 1.4; and (3) roundness is about 0.93 to about 1, about 0.95 to about 0.99 (eg, Sysmex FPIA). When measured with a 2100 analyzer).

0085The characteristics of the toner particles may be determined by any suitable technique and equipment (eg, Beckman Coulter MULTISIZER 3). The particle size range and particle size distribution can be obtained in this way. The particle size distribution gives the ratio of fine and coarse particles to the desired average particle size. The measured value of the content of coarse particles is VD.₈₄It is a metric, in which case the coarse particles are greater than 84% in particle size. Another metric for assessing the content of coarse particles is VD₈₄/ VD₅₀It is a ratio, and a value of 1.23 or less, 1.22 or less, 1.21 or less, or less is an indicator that the amount of coarse particles is small and acceptable. The measured value of the content of fine particles is ND₁₆It is a metric, in which case the particles are smaller than 16% in particle size. Another metric for assessing particulate content is ND₅₀/ ND₁₆A ratio of 1.30 or less, 1.29 or less, 1.28 or less, or less is an indicator that the amount of fine particles is small and acceptable. Depending on the thermal process for producing the resin, the fine particle content may be low, the coarse particle content may be low, or both.

0086The production of toner is improved by using the desired heat-treated latex. For example, the throughput, which is a measured value of toner production per unit time, becomes large when the target heat-treated resin is used. Generally, the toner throughput is about 600 kg / hour. The target magenta toner containing the heat treated resin has a throughput of at least about 700 kg / hour, at least about 750 kg / hour, and at least about 800 kg / hour.

0087The yield is estimated to be either 100% reaction efficiency or known conventional efficiency values to obtain the expected amount of product and may be a theoretical calculation based on the input amount. .. Compare the actual amount of product with the expected amount. Alternatively, the yield may reflect the conventional average of the products produced. The yield of toner that carries out the method of the present invention is improved when the desired heat-treated resin is used. Yields are generally at least about 1.5% higher than those observed when the resin used for the toner is not heat treated (ie, the resin produced by PIE without the heat treated solvent stripping step). , At least about 1.75% larger, at least about 2% larger, at least about 2.25% larger, at least about 2.5% larger, or larger. At the level where the toner is commercially manufactured, a 1% increase in yield is, in other words, an increase of about 17 kg of dry toner per batch, a yield of 1700 kg of dry toner from a 3000 gallon reactor. When the method of the present invention is carried out, a yield increase of about 2% is obtained.

0088Not only considering the production of latex, but also considering the EA process itself, the processing time is shortened. This is because the heat treatment shortens the production time and production conditions of the resin for preparing the surface of the latex particles in order to improve the aggregation. The increase in yield has a 1: 1 inverse correlation with the reduction in processing time. The processing time for commercial implementation is at least about 1.5% shorter, at least about 1.75% shorter, and at least about 2 than would be observed if the resin used for the toner was manufactured by PIE without heat treatment during the solvent stripping process. % Weak, at least about 2.25% weak, at least about 2.5% weak, or shorter. Therefore, a 2% increase in yield corresponds to a 2% reduction in overall processing time, and in commercial production, implementation would be less than about 10 hours in 20 batch intensive production over 4 days.

<p num="0089"> The subject is illustrated by the following non-limiting example. Parts and percentages are by weight unless otherwise specified.</p><p num="0090"> (Example 1 Latex production) Latex is produced using phase inversion emulsification (PIE) using LMW amorphous polyester resin and HMW amorphous polyester resin. The polyester resin is dissolved in a mixture of MEK and IPA, DIW (I) and ammonia (I). Ammonia (I) is used to neutralize the polyester and promote dispersion of the resin in the mixture of organic solvent and DIW (I). Ammonia (II) is then added to this homogeneous resin solution, followed by DIW (II) and phase inversion to create a uniform suspension of polyester particles in the aqueous continuous phase. The formulations of these two emulsions are presented in Tables 1 and 2.</p><p num="0091"><tables num="1"><img id="000002" he="80" wi="170" file="JP2016014875A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0092"><tables num="2"><img id="000003" he="77" wi="170" file="JP2016014875A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0093"> (Example 2 heat treatment) The latex of Example 1 was split into two distillation apparatus. One distillation apparatus has a conventional heating jacket set at 58 ° C and the other has a jacket set at 65 ° C, which temperature is the Tg of HMW resin and LMW resin. taller than. Distillation was continued until the content of volatile organic compounds (VOCs), as determined by gas chromatography (GC), fell below about 300 ppm. The distilled latex was then lyophilized and characterized. Table 3 lists the properties of latex distilled at 58 ° C and 65 ° C.</p><p num="0094"><tables num="3"><img id="000004" he="80" wi="170" file="JP2016014875A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0095"> During the distillation process in which the desired method is carried out using a jacket temperature of 65 ° C, the latex particles have a temperature of T of the latex particles._gIt will soon be in good contact with the higher vessel surface. Since the solvent was continuously distilled under reduced pressure, the solvent evaporated. A stable batch temperature of about 45 ° C was obtained due to cooling by evaporation, which removes heat from the reactor. Therefore, when brought into contact with the inner surface of the container with agitation, only the latex particles undergo a rapid and temporary heat treatment.</p><p num="0096"> This data shows that high jacket temperature is a property of latex that is widely believed to be important for toner composition and properties (eg particle size, T)._gAnd molecular weight) will not be adversely affected. Therefore, the jacket temperature is 65 ° C. A significant portion of the steric barrier on the surface of the latex particles was removed without including the properties of the latex, as will be apparent with the toner of Example 3 below. This temperature distilled the solvent more quickly, shortened the distillation cycle time by 25% and reduced production costs.</p><p num="0097"> (Example 3 Manufacture of toner using heat-treated latex) Magenta toner is the most difficult toner to produce due to its poor yield and very wide geometric particle size distribution (GSD) (both coarse and fine particles) compared to other colors. The problem may have something to do with red colorants.</p><p num="0098"> Magenta core-shell toner was manufactured by standard EA procedures. The resulting toner contained 39% LMW amorphous polyester resin, 39% MHW amorphous polyester resin, 7% crystalline polyester resin, 9% wax and 6% magenta colorant. .. Amorphous resins were produced by standard PIE processes or by heat treatment during distillation as taught herein.</p><p num="0099"> When heat-treated latex was used in the production of magenta toner, the yield exceeded 96%. This was unpredictable, especially given the small number of batches completed this month (7 batches compared to an average of 12 / month in the previous 5 months). Overall yields are generally positively correlated with the overall length of centralized production and the number of batches produced during this centralized production, and longer intensive productions are usually overall. Yield is higher. When using control latex, the average yield of magenta toner was generally about 93%. Yields of magenta toner were higher than those of black, cyan and yellow toner this month.</p><p num="0100"> After observing the increase in yield, the data were further analyzed under a shorter intensive production period. The main reason for the improvement in yield is D due to volume._84/50The overall coarse particle content was found to be about 0.004 units smaller than the 4-month average and 0.002 units smaller than the previous low values during this period. The yield increase due to the reduced coarse particle content was 0.005 units higher than the nominal average production yield over the year. Overall coarse particle content (VD)_84/50) Was reduced, and less toner was lost in the wet sieving process (excess coarse particles were collected and discarded).</p><p num="0101"> (Example 4 Improvement of cycle time) As much as an increase in yield, this process would be counterproductive to efficient and economical production if it did not provide at least as much or higher throughput as the standard process. From the data, the highest throughput in the last month (800 kg / hour) compared to the monthly average of less than 600 kg / hour for magenta toners made with traditionally manufactured resins or toners of other colors. Time) was found to be obtained with magenta toner using heat treated latex. It is unpredictable (due to polyester's high affinity for water) that in manufacturing equipment, when the humidity is high, production during the summer months reduces the ability to dry polyester particles. .. Unexpectedly, the highest throughput was obtained with heat treated latex, as well as further environmental challenges, which, surprisingly, occurred in lots of magenta toner.</p>