TW200405141A - Process for producing toner for electrostatic image development - Google Patents

Abstract

This invention provides a process for producing a toner for electrostatic image development composed of microcapsule toner particles, the microcapsule toner particles each comprising a core material constituted of a binder resin composed of a colorant and an olefinic copolymer of ring structure and, covering the core material, an outer shell material constituted of a binder resin, characterized in that fine particulate liquid drops of a solution comprising a good solvent solution of binder resin for constituting the core material and, dispersed therein, a colorant is injected and delivered into a poor solvent solution of binder resin for constituting the outer shell material so as to effect encapsulation. The thus produced microcapsule toner is satisfactorily applicable to not only low-temperature thermal fixing but also pressure fixing and hot roller fixing systems capable of realizing high-speed copying. Further, the microcapsule toner can solve problems of conventional microcapsule toners, excels in storage stability and offset development prevention, and can realize uniform particle size distribution which enables hue of high density.

Description

200405141 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to the electrostatic charge of a pressure fixing type and a heating roller fixing type (hereinafter sometimes referred to as "pressure heating type" or "pressure heating method") Method for manufacturing toner for image development.

In detail, the present invention relates to a method for manufacturing a toner, which comprises a dry magnetic one-component system, a dry non-magnetic single-component system, a dry two-component system, and a liquid-dry system. The liquid toner-based developer can be fixed by pressure when it is fixed on a copied substrate such as paper or film, or when it is fixed by a heating roller. It has sufficient fixability, toner waste and transparency, and can form sharp images. In addition, the invention also has a method for manufacturing toner, which can sufficiently ensure that the image will not be offset (offset). In the field (non-offset temperature field), it has excellent high-speed fixability and storage stability, and is used as a practical developer.

In addition, the present invention relates to the above toner which can be widely used in photocopiers, printers, facsimile machines, color photocopiers, color laser photocopiers, color laser printers, and electrophotographic high-speed printers. [Previous technology] Against the background of the rapid expansion of office automation, the improvement of mechanical shock resistance in response to the rapid printing speed of electrostatic charge imaging photocopiers and printers, and in response to high-grade, sharp pictures Imaging, low-temperature fixability, and reproduction of images due to the excellent light transmittance of corresponding color toners are increasingly demanded. -5- (2) (2) 200405141 In order to meet the needs of such high-speed reproduction and high-quality images, there must be a non-offset temperature range that can adequately meet the physical strength of toner particles and low-temperature fixation, and it is expected that there is no need to fix the fixing roller (fixation r 〇11) Supply oil and realize non-sticking form without contaminating the copied substrate. Toners require performance in all aspects such as chargeability, fixability, abrasion resistance, portability, storage stability (after a long time, toner particles are not easy to agglomerate or become lumpy), etc. When the previous method was dry-mixed in a mixed manner, there was a limit to meeting all requirements. That is, in order to respond to the above-mentioned needs, toners must be provided with various opposite functions. To solve the above-mentioned problems, a core material (core substance) particle of a so-called core has been created in a so-called shell. The shell material (shell material) is a microcapsule toner that is constructed by covering and packaging. Using the microcapsule toner method, for example, the fixability is good, but the storage stability is deteriorated. Therefore, a binder resin that is prone to shifting is used as the core material. On the other hand, storage stability or non-shifting is used. Good adhesive resin is the material of the shell, which can solve the opposite requirement. There have been various inventions and creations of such functionally separated microcapsule toners. For example, Japanese Unexamined Patent Publication No. 9-2 92 73 5 discloses a film fixing and heating type image forming apparatus using a microcapsule toner manufactured by a suspension polymerization method, and an example using the same manufacturing method is disclosed in Japanese Kaisho SPSS 8 56 and JP 5 9 — 6 1 8 4 2. In addition, Japanese Patent Publication No. 5 6 — 1 3 94 5 proposes the toner production method using the spray drying method (3) (3) 200405141, and Japanese Patent Publication No. 8-1 6 793 proposes the use of the water phase separation method to produce micro A method for encapsulating toner, and Japanese Patent Application Laid-Open No. 3-5 69 70 proposes a method for forming a microcapsule toner by using a high-pressure homogenizer to form a microcapsule toner after forming a shell layer by in-situ polymerization. In addition, an interfacial polymerization method, a coacervation method, and a dry capsule method have been introduced. In Japanese Patent Application Laid-Open No. 10-1 077 8 for the purpose of improving the charging, it is revealed that the resin and the solvent will be dispersed by itself. A method of inverting and emulsifying a mixture composed of a colorant in an aqueous medium to produce a capsule toner. Such a method of manufacturing a capsule toner by a phase inversion emulsification method is also disclosed in JP-A 11-65 1 68, JP-A 10-207 1 1 9 and JP-A 1-2-3 3 1 5 69. . Japanese Unexamined Patent Publication No. 10—7 8 6 7 6 uses an amorphous polyester having an acid rhenium of 9.5 (mg KOH / g) in the resin for the outer shell of a capsule to improve antiblocking properties. In addition, Japanese Patent Application Laid-Open No. 10-22 22 13 provides storage elasticity of capsule toner manufactured by the in-situ polymerization method to improve low-temperature fixability and offset resistance. Japanese Patent Application Laid-Open No. 10-3 0 1 3 describes that a toner having a specific amount of a capsule structure having a specific amount of a resin component soluble in a mixed solvent is used for electrostatic charge imaging development, resulting in low-temperature fixability and high image quality. Japanese Patent Application Laid-Open No. 2000-5 65 10 proposes a method for manufacturing a capsule toner having a low fixing temperature containing a coloring agent polymerizable monomer composition in an aqueous dispersion medium, which is described in Japanese Patent Laid-Open No. 2000-9-9662 The capsule toner made of ε-caprolactone ring-opening polymer is suitable for low fixing temperature. -7- (4) (4) 200405141 In JP 2000-112175 and JP 2000-112176, it is proposed to dissolve a binder resin in a dispersion liquid of crushed toner particles to produce a capsule toner having excellent fixing characteristics. Method. In addition, capsule toners for the purpose of improving low-temperature fixability or storage stability have been proposed in Japanese Patent Application Laid-Open No. 11-305478 and Japanese Patent Application Laid-Open No. 2000-284525. However, in these prior art toner manufacturing methods, except for the spray drying method, water is used as a medium. Therefore, it is troublesome when drying, and it is not enough to produce microcapsule toner on an industrial scale. In addition, when the spray-drying method is used, the desired average particle diameter is kept to be generally 10 μm or less, so that it is not easy to be micronized. Under these circumstances, the present inventors have disclosed in the nuclear material that the Japanese Patent Application No. 10-3 1 2 2 15 (Japanese Laid-Open Patent Publication No. 2 0 0 — 1 4 7 8 2 9) can be incorporated into the nuclear material. According to the invention concerning toner for electrostatic charge image development according to the above requirements, the invention has a binder resin having a glass transition temperature in a range of -20 ° C to 60 t and a number average molecular weight in a range of 100 to 20,000. Ring-shaped olefin copolymer, and / or glass transition temperature of 60 ° C or more and 180 ° C or less when the shell material is incorporated as an adhesive resin, and the number average molecular weight is 1,000 or more Microcapsule toner particles made of olefin copolymers with a cyclic structure up to 1,000,000. However, the manufacturing method of the microcapsules disclosed in the above invention is to use the usual re-sinking method, that is, a good solvent solution of the binding resin constituting the nuclear material, and the nuclear material solution in which the colorant is dispersed in the solution is dropped into the composition. In the weak solvent solution of the binding resin of the shell material, the solution of the shell material is deposited around the core material. Θ12 -8- (5) (5) 200405141 The toner cannot completely suppress the variation of the particle diameter β within a specific range, and there is a problem that the toner having a sharp particle size distribution cannot sufficiently respond to the demand for industrial scale supply. SUMMARY OF THE INVENTION The subject of the present invention is to provide a method for manufacturing a microcapsule toner with uniform particle size distribution, which can fully respond to the pressure fixing method and the heating roller fixing method for achieving low-temperature heating and fixing or high-speed reproduction, Moreover, it solves the problems of the previous microcapsule colorants. In addition, it has storage stability and excellent anti-offset phenomenon, and can exhibit high-concentration color and uniform particle size distribution. The inventors have mixed the olefinic polymers having two cyclic structures with different glass transition temperatures and number average molecular weights as the static electricity of the binder resin constituting the core material and / or the shell material of the microcapsule color powder particles. In the manufacture of toner for image development, when the nuclear material solution is dropped into the shell material solution, 'the droplet is sprayed from the nuclear material solution into the shell material solution and encapsulated as particulate droplets. It has been found that the above problems can be solved. The present invention has been completed. That is, the present invention relates to a method for producing a toner for electrostatic charge image development, which is a core material formed of a binder resin containing a colorant and an olefin copolymer having a cyclic structure, and a binder resin The toner composed of the microcapsule toner particles formed by covering the core material and forming the shell material is characterized in that fine particles of the nuclear material solution in which the colorant is dispersed in a good solvent solution constituting the binding resin constituting the nuclear material The liquid droplets are ejected and dripped into a weak solvent solution of (6) (6) 200405141 adhesive resin constituting the shell material to be encapsulated. At the same time, the manufacturing method of the toner described above is characterized in that: a spray nozzle or a nozzle for an ink jet printer is used to spray particulate droplets of a nuclear material solution into a solution of a shell material. Other features include: The method of spraying the nuclear material solution using the nozzle of the inkjet printer is selected from the piezoelectric element volume change, the electric field control using the multi-electrostatic electrostatic method, and the thermal element volume change. Either method; When using nozzles for inkjet printers, the solvent of the nuclear material solution is a mixture of aliphatic hydrocarbons and alicyclic hydrocarbons, that is, naphthenic solvents; the binding resin constituting the nuclear material has a glass transition temperature greater than -20 ° C less than 65 ° C and cyclic structure olefin copolymer with weight average molecular weight greater than 200 and less than 40,000 Anhydride modification, ideally copolymers modified with acrylic acid or maleic anhydride; the adhesive resin constituting the shell is a glass transition temperature of more than 60 ° C and less than 180 ° C, and a weight average molecular weight of more than 2000 and less than 200,000. It is formed by an olefin-based copolymer having a cyclic structure; the olefin-based copolymer resin constituting the cyclic structure having a shell material is modified with a carboxylic acid or a carboxylic anhydride, and is ideal It is a copolymer modified with acrylic acid or maleic anhydride; a mixture of rhenium is used in the binder resin constituting the core material and / or the binder resin constituting the shell material; and -10 ... (7) (7) 200405141 鱲It is selected from the group consisting of fatty ammonium wax, oxidized polyethylene wax, and acid-denatured polypropylene wax 'and a mixture of oxidized and non-oxidized polyethylene wax. At least-filial piety. In addition, the present invention relates to a toner for developing an electrostatic charge image, which is characterized in that the surface of the microcapsule toner particles produced by the above-mentioned toner manufacturing method is additionally added or coated with fine silica dioxide powder. The present invention is described in detail below. [A] Material of the core material constituting the microcapsule toner particles The core material includes a binder resin and a coloring agent as essential materials, and may further include a function imparting agent, a charge adjusting agent, and other additives as optional components. (1) The binding resin and the coloring agent together constitute the core material part of the microcapsule toner, that is, the binding resin of the core material is an olefin polymer having a cyclic structure, or a cyclic polymer having a cyclic structure. A mixture of an olefin polymer and a binder resin for heat fixing and / or a binder resin for pressure fixing described below. These have lower melting points or softening temperatures and higher fixing properties than the adhesive resins used to form the casing material described later. Examples of the heat-fixing adhesive resin include polystyrene, styrene polymers such as substituted polystyrene, styrene-acrylate copolymers or styrene-methacrylate copolymers, and styrene-acrylonitrile copolymers. Materials such as styrene polymers, poly (meth) acrylic resins or acrylic resins such as poly (meth) acrylate resins, polyester resins, and epoxy resins.

-11-(8) (8) 200405141 Combined use of two or more. On the other hand, examples of the pressure-setting adhesive resin include plant-based, animal-based, mineral-based, and petroleum-based waxes (specific examples include carnauba wax, water-containing wool wax ', beeswax, montan wax, paraffin wax, and microcrystals. Waxes, etc.), higher fatty acid derivatives (for example, stearic acid, hexadecanoic acid, oleic acid, lauric acid, and other polyvalent alcohols and calcium stearate, zinc stearate, lead stearate, stearic acid Metal salts of higher fatty acids such as magnesium). Polyolefin wax (for example, polyethylene wax, polypropylene, etc.), olefin alone or copolymer (for example, ethylene- (meth) acrylic copolymer, ethylene- (meth) acrylate copolymer, ethylene-acetic acid Ethylene copolymers, ionic resins, etc.), styrene resins (eg, low molecular weight polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, etc.), epoxy resins, and polyester resins, And these can be used alone or in combination of two or more. In order to introduce the low-temperature fixation method for high-speed copying to obtain high-quality sharp images, it is necessary to have the exact fixity of the pressure heating fixation (thermocompression) method. Therefore, the fixation must be based on the above fixation. The method appropriately selects the type and composition of the adhesive resin. From the viewpoint of expanding the non-offset temperature range where no offset phenomenon occurs and improving non-offset properties, the use of cyclo olefin copolymer (COC) with the following cyclic structure as the core material An adhesive resin is desirable. As a core material, an olefin-based polymer having a cyclic structure has a higher degree of fixation than a shell material, so the glass transition temperature (Tg) must be in the range of -20 ° C to 65t, and the number average molecular weight (Μη) is in the range of 100 or more and -12-Ό'ΪΌ 200405141 〇) 2 0 '0 0 0 or less. If the glass transition temperature is lower than -20 ° C, the viscoelasticity will increase and the printed image will be sticky. On the other hand, if the glass transition temperature exceeds 65 ° C, it will be too rigid to obtain a sufficient fixation. Sex. In addition, if the number average molecular weight is less than 100, sufficient fixability cannot be obtained. On the other hand, when the number average molecular weight exceeds 20,000, it is difficult to dissolve in a solvent, which is a problem in practical use. The so-called glass transition temperature (Tg) is the temperature corresponding to the intermediate point representing the shift of the transition heat in the differential scanning calorimetry (DSC), and the number average molecular weight (Μη) is the gel permeation chromatography (GPC) The tritium ′ measured in terms of standard polyethylene or polystyrene is more specifically a tritium obtained by measurement under the following conditions. Use column: JORDI-SAEULE 500x1 〇 Linear (Mobile) mobile phase: 1,2-dichlorobenzene (135t :), mobile 0.52 / minute detector: differential refractive index The following details for olefin polymers with ring structure As described below. The olefin-based polymer having a cyclic structure is a lower olefin (α-olefin, acyclic or olefin in a broad sense) having a carbon number of 2 to 12, preferably 2 to 6, and a carbon number of 3 to 17, preferably It is a copolymer of a cyclic and / or polycyclic compound (cycloolefin) having at least a double bond of 5 to 12 (cycloolefin), and a colorless and transparent transmissivity. Examples of the lower olefin constituting the polymer include ethylene, propylene, butene, and examples of the cyclic olefin include norbornene 'tetracyclododecene, biscene, and cyclohexane. The olefin-based polymer having the cyclic structure is catalyzed by, for example, using a metallocene system! 1. Ziegler catalyst and metathesis polymerization-13- (10) (10) 200405141 (Metathesis polymerization), that is, polymerization using the polymerization method of double bond opening and ring-opening polymerization catalyst Thing. Examples of the synthesis of olefin-based polymers having this structure are disclosed in Japanese Patent Application Laid-Open No. 5-339327, Japanese Patent Application Laid-Open No. 5-9223, Japanese Patent Application Laid-Open No. 6-27 1 628, European Patent Publication (A) No. Instruction No. 203799, the same as Instruction No. 407870, in the same as Instruction No. 283 1 64, in the same as Instruction No. 1 56464, and in Japanese Patent Application Laid-Open No. 7-2533 15. According to the above literature, one or more monomers of the above-mentioned cyclic olefins may be -78 to 150 ° C, preferably 20 to 80 ° C and a pressure of 0.01 to At 64 bar, it is polymerized in the presence of a co-catalyst such as aluminoxane and a catalyst formed from at least one of the formed metallocene, for example, a pin. Other useful polymers are described in European Patent Publication (A) No. 3 1 7262. Hydrogenated polymers and copolymers with styrene and biscene can also be used. In a state in which a metallocene catalyst is dissolved in an inert hydrocarbon of an aliphatic or aromatic hydrocarbon, since the metallocene is activated, for example, the metallocene catalyst is dissolved in toluene to perform preactivation and reaction in a solvent. Important properties of olefin-based polymers having a cyclic structure are softening temperature, melting point, viscosity, dielectric properties, non-offset temperature range, and transparency. These properties can be advantageously adjusted depending on the type of monomer or comonomer or the ratio of comonomers to each other, molecular weight, molecular weight distribution, hybrid polymer, blend, and selection of additives. In addition, the molar ratio of the reaction between acyclic olefins and cyclic olefins can be changed widely depending on the olefin-based polymer having the intended cyclic structure. -14- (11) (11) 200405141 : 1 to 1: 50, preferably 20: 1 to 1: 20. For example, when the non-polymer component introduces ethylene as an acyclic olefin, and introduces A norbornene M as a cyclic burning tobacco, which reacts with a total of two compounds, an olefin polymer having a cyclic structure of a counter product The glass transition temperature (Tg) is greatly affected by these introduction ratios. If the content of norborn burnt is increased, Ij Tg also tends to go up and down. For example, if the borneol is adjusted to a composition of 15 mol% or less (85% of Ecan), a copolymer having a Tg of -20 ° C to 65 ° C can be obtained. If the norbornene is adjusted to 15 mol% or more, a copolymer having a Tg exceeding 65 ° C and less than 180 ° C can be prepared. The physical properties of the number average molecular weight can be adjusted by conventional methods in the literature. The olefin-based polymer having a cyclic structure used in the present invention is constituted as follows. That is, the binder resin as the core material is composed of an olefin polymer having a cyclic structure acid-modified with an olefin polymer having a non-denatured cyclic structure at a weight ratio of 95: 5 to 5: 95. should. The number-average molecular weight of the olefin polymer having such a non-modified cyclic structure (Mη; measured by GPC in terms of polyethylene, the same applies hereinafter) is 100 or more and 20,000, or preferably 1,000 or more and 10,000 or less. The weight average molecular weight (Mw) is 200 or more and 40,000 or less, preferably 6,000 or more and 30,000 or less, and the glass transition temperature (Tg) is -20 ° C or more and 65 ° C or less, and preferably 40 ° C or more and 65 ° C or less. On the other hand, the number-average molecular weight (Mη) of the olefin-based polymer having a cyclic structure modified by using the olefin-based polymer containing the above-mentioned unmodified cyclic structure as a base resin acid is 100 or more and 20,000 or less, preferably Above 1,000, below 10,000, weight average molecular weight (Mw) of 300 or more, 80,000 or less, preferably 3,000 or more and 40,000 or less, and glass transition temperature (Tg)-20 ° C or more 65 (12 (12) 200,405,141 C or less, preferably 40 ° C or more and 65 ° C or less, and acid hydrazone is 5 to 50. In order to ensure the fixability, and to provide sufficient practicality, the composition of the above-mentioned olefin-based polymer having a cyclic structure in the offset temperature range is preferably as described below. That is, it is composed of a low molecular weight polymer or polymer fraction (a) having the following physical properties and a high molecular weight polymer or polymer fraction (b). That is, the olefin-based polymer having a cyclic structure may be a mixture of polymer (a) and polymer (b), or a polymer having a peak molecular weight distribution and having a number average molecular weight of less than 7,500. Part with a polymer part having a number average molecular weight of 7,500 or more, or a molecular weight distribution with two or more peaks, of which a polymer having at least one peak has a number average molecular weight of less than 7,500, and a polymer having other peaks Some have a number average molecular weight of 7,500 or more. The reason why an olefin polymer having a cyclic structure is composed of a polymer or polymer portion (a) of low viscosity (low molecular weight) and a polymer or polymer portion (b) of high viscosity (high molecular weight) is because The expansion of the offset temperature range to both the high and low temperature side will improve the toner fixation at high speed copying, and change the fixation at low temperature and low pressure. The number average molecular weight of the polymer or polymer portion (a) (hereinafter abbreviated as a) (measured by GPC (gel permeation chromatography) converted to polyethylene, the same applies hereinafter) is less than 7,500, preferably 1,000 to 7,500 or less, more preferably 2,000 to 7,500 or less, weight average molecular weight of less than 1 5,000, preferably 1,000 to 1 5,000 or less, more preferably 4,000 to 1 5,000 or less, limiting viscosity (iv · the polymer 1.0 The inherent viscosity at 135 ° C when uniformly dissolved in decalin 100 J) is -16-

Γν ^ A (13) (13) 200405141 is less than 0.25d ^ / g, and the glass transition temperature (Tg) is preferably lower than 70 ° C. On the other hand, the number average molecular weight of the polymer or polymer portion (b) (hereinafter referred to as component b) is more than 7,500, preferably 7,500 to 50,000, and the weight average molecular weight is 1 5,000 or more, preferably 1 5,000 to 50,000, and the limiting viscosity (iv) is 0.25 d < / g or more. In addition, the content of the component b is less than 50% by weight of the entire binder resin, and more preferably 5 to 35% by weight. Component b imparts structural tack to the toner to improve the anti-offset effect or the adhesion to the copied substrate such as paper film, but if the content exceeds 50% by weight, its uniform kneading property will be extremely reduced and it will cause problems for the toner. . That is, it is not easy to obtain high-quality, sharp images with high fixing strength and excellent heat response, mechanical pulverization is reduced, and it is technically difficult to obtain the particle size necessary for toner. In addition, "the polymer or the polymer part herein" means that when an olefin polymer having a cyclic structure is composed of a mixture of various components such as various number average molecular weights, it is each polymer component before mixing, except in this case In order to distinguish the polymer that is finally synthesized by an appropriate method such as GPC. When the polymer portions are monodisperse or nearly monodisperse, a so-called number average molecular weight (Mη) of 7,500 is approximately equivalent to a weight average molecular weight (Mw) of 15,000. In order to expand the non-offset temperature range to the low-temperature side, it is necessary to rely on the low-viscosity component a constituting the olefin polymer having a ring structure. On the contrary, to expand to the high-temperature side, it is necessary to rely on the high-viscosity component b. In order to more effectively expand the non-offset temperature range to the high temperature side, it is desirable to have a high viscosity component b having a number average molecular weight exceeding 20,000. When the whole binder resin is 100 weight points, the content of components a and b constituting the olefin polymer-17- (14) (14) 200405141 should preferably be 0.5 weight points or more, especially 5 to 1 weight. Divided into ideals. If both sides are less than 0.5 weight percent, it is difficult to obtain a wide non-offset temperature range in practical use. Because olefin polymers with high viscosity (high molecular weight) and low viscosity (low molecular weight) having a cyclic structure have the number average molecular weight (Mη), weight average molecular weight (Mw), and limiting particle size (iv), which indicates the molecular weight distribution. The dispersion of Mw / Mn is as small as 1 to 2.5, that is, because monodisperse and close to monodisperse, the thermal reaction is fast, so toners with strong fixing strength can be manufactured. Not only can the toner be fixed at low temperature and low pressure, In addition, it contributes to the toner's stable image retention, widely discarded toner, uniform charge distribution, or electrical stability that indicates the fixation of charging and static elimination efficiency. Here, especially when the polymer or polymer portion of the low viscosity is monodisperse or nearly monodisperse, it means that the so-called toner has excellent heat response properties such as instantaneous melting and solidification characteristics. Also, because The olefin-based polymer having a cyclic structure is colorless, transparent, and has high light transmittance. Therefore, even if the three primary color pigments of yellow, blue, and red are added, they can maintain sufficient transparency and have been applied to color toners. In addition, the olefin polymer has a very small heat of fusion in the measurement by DSC method (differential scanning calorimetry), and the energy consumption when fixing the toner can be greatly reduced. Furthermore, by introducing a carboxyl group to an olefin polymer having a cyclic structure, that is, acid modification using a carboxylic acid or carboxylic anhydride, it is possible to improve the compatibility with other resins and the dispersibility of the pigment in the toner. With the introduction of such carboxyl groups, the adhesion of the toner to the copied substrate such as paper or film can be improved and the fixability can be enhanced. -18- (15) (15) 200405141 The method for introducing a carboxyl group is preferably a two-stage reaction method in which an olefin polymer having a cyclic structure is first prepared and then a carboxyl group is introduced. There are at least two methods for introducing this carboxyl group. One is to oxidize an alkyl group such as a methyl group at the end of a polymer by a molten air oxidation method as a carboxyl group. However, in this method, when an olefin-based polymer having a cyclic structure synthesized with a metallocene catalyst is hardly branched, it is difficult to introduce a large number of carboxyl groups. Specifically, a carboxylic acid or carboxylic anhydride, preferably maleic anhydride, acrylic acid or methacrylic acid, is polymerized with a peroxide such as t-butanol peroxide as an initiator to introduce a carboxyl group. The olefin-based polymer having a structure preferably has a graft ratio of 1 to 5% by weight, and more preferably 3 to 5% by weight. If it is less than 1% by weight, the above-mentioned effects such as improvement in compatibility are not significant. On the other hand, if it exceeds 5% by weight, intermolecular cross-linking occurs in the hydrocarbon-burning polymer to increase the molecular weight, so that the kneading property and the pulverizability become ineffective It is practical, has extremely yellowing, and disappears transparently. It tends to be unsuitable for toners that require colorless transparency. Furthermore, amino groups can also be promoted in the same way by introducing hydroxyl groups using conventional methods. In addition, in order to improve the fixability of the toner, a crosslinked structure may be introduced into the olefin-based polymer having a cyclic structure. One of the introduction methods of the cross-linked structure is to add pentamyl, cyclohexanylamine, norbornadiene, tetracyclic and ten simultaneously with acyclic olefin and cyclic olefin during the polymerization of the olefin-based polymer. Diene monomers such as dicarbadiene and butadiene undergo terpolymerization. By this method, although the olefin polymer has no cross-linking agent, it also has an active terminal, and can have its function by a conventional chemical reaction such as oxidation, epoxy action, or by adding a cross-linking agent to have a cross-linked structure. . -19- (16) (16) 200405141 Others. The cross-linking method is to add metals such as zinc, copper, and calcium to an olefin polymer having a cyclic structure incorporating the carboxyl group, and then mix and melt them with a biaxial extruder. 'The metal is dispersed as fine particles in the polymer as an ionic resin (Ionomer) to impart a crosslinked structure. For the purpose of the ionic resin technology, for the purpose of obtaining toughness, it has been disclosed (US Patent No. 4,693,941) that a ternary copolymer of carboxyl-containing ethylene is partially or completely neutralized to form a divalent metal salt. Japanese Patent Publication No. 6-500348 proposes that about 20 to 80% of the residual acid groups of a polyester resin molded product of an ionic resin containing an unsaturated carboxylic acid be zinc, cobalt, nickel, or aluminum for the same purpose. Or copper (Π) neutralizer. The core material may be added to an olefin-based polymer having a cyclic structure with 5 to 95% by weight of an olefin-based polymer having an introduced carboxyl group, that is, an olefin-based polymer having a cyclic structure modified with an acid. This addition is an effective means to ensure a non-offset temperature range. (2) Colorants Colorants can be mixed in the core material with carbon black, diazo yellow, phthalocyanine blue, wow acridone, carmine 6 B, and azo red previously used in monochrome or color toners. , Perillene, etc. (3) Function imparting agent In order to expand the non-offset temperature range to improve the non-offset property of the toner, various polar or non-polar waxes can be mixed as the function imparting agent. Here, examples of the polar wax include ammonium wax, garopa wax, higher fatty acids and esters thereof, higher fatty acid metal soaps, partially alkalized higher fatty acid esters, higher aliphatic alcohols; on the other hand -20- (17) ( 17) 200405141. Examples of non-polar waxes are polyolefin waxes and paraffin waxes. At least one wax can be selected as a function imparting agent from these. From the perspective of the wide range of non-offset temperatures that can be obtained, among the various waxes, the mixture of fatty acid amidamine, oxidized polyethylene wax, acid-modified polypropylene wax, and oxidized and non-oxidized polyethylene wax is ideal. In order to expand the above-mentioned non-offset temperature range of the toner to improve the toner performance, the ideal wax application method is as follows. That is, the melting point (peak temperature in differential scanning calorimetry (DSC)) is in the range of 80 to 140 ° C, and it is desirable to use two waxes having different melting points. If the melting point does not exceed 80 ° C, there is a tendency that blocking problems due to low-melting substances occur when the toner is made. On the other hand, the function imparting agent must be completely melted when it exceeds the softening temperature of the binder resin, and is therefore softened by an olefin-based polymer having a cyclic structure containing the main component of the binder resin (about 1 3 to 5 to 1). 4 0 ° C). The upper limit of the melting point is preferably 140 ° C. Specifically, two kinds of fatty acid fluorene-based or hydrocarbon-based waxes exemplified below can be used. ① Waxes with various polar groups. Various fatty acid ammonium waxes, such as monoammonium arachidite (melting point n OOc), monoammonium behenate (melting point 115 ° c), N, N, -dioleyl sebacin Amidoamine (melting point 1 15 ° C) 'N, N' —Dioleamide adipate (melting point n9t), Ν, Ν · monostearic acid isophthalamide (melting point 1 29) ), Oxidized hydrocarbon waxes, such as' oxidized polyethylene wax (melting point u 6 it), acid-modified polyolefin wax, for example, acid-modified polypropylene wax (melting point 138t), carnauba wax (melting point about Sichuan ^ ), A mixture of oxidized and non-oxidized polyethylene wax. ② Non-polar (non-polar group) wax

& 2S _21-(18) (18) 200405141 The olefin waxes of hydrocarbon waxes are, for example, polyethylene wax (melting point 130 ° C), polypropylene wax (melting point 120 to 150 ° C), paraffin wax (melting point about 60 to 80 °) C), SASOl wax (freezing point is about 98 ° C), microcrystalline wax (melting point is about 80 to 100 ° C). In addition, as a function-imparting agent for preventing displacement, the silicone oil (Silicone 011) and the wax mentioned above can be used as long as the effect of the present invention is not impaired. (4) Charge modifiers Previously known charge modifiers, such as nigrosine dyes, fatty acid modified nigrosine dyes, metal containing nigrosine dyes, metal fatty acid modified nigrosine dyes, 3,5-di-t-butyl Chromium salicylate, quaternary ammonium salt, triphenylmethane dye, azochrome complex, etc. can be mixed in the core material. In addition, as described later, when the charge modifier is mixed with the shell material, the mixing with the core material can be sacrificed. (5) When necessary, other additives are mixed with colloidal silica (including aerosol silica), alumina, titanium oxide, etc. in the toner constituents to the extent that the effect of the present invention is not impaired. Chemical agents, or lubricants composed of fatty acid metal salts such as barium stearate, calcium stearate, barium laurate and the like. (6) Mixing amount of each component The mixing amount of the above components in the nuclear material is the same as the general formula of electrostatic charge image developing color printers and toners for printers' as shown in the table below. -22- (19) 200405141 Table 1 General composition of various toners Binder resin colorant Dry type 2 component system 50-100 0 ~ 20 Dry type non-magnetic unit system 50 ~ 100 0 ~ 20 Dry type magnetic unit system 0-100 0 ~ 20 Dry polymerization system 50 ~ 100 0 ~ 20 Liquid dry toner 15 ~ 50 0 ~ 10 Liquid toner 15 ~ 50 0-10 Unit: (% by weight) Charge modifier function imparting agent Magnetic powder solvent 0 ~ 10 0 ~ 20 one — 0 to 10 0 to 20 one — 0 to 10 0 to 20 0 to 60 — 0 to 10 0-20 — — 0 to 5 0 to 10 one 50 to 70 0 to 5 0 to 10. — 50 to 70 [B] Materials constituting the shell material of the microcapsules " powder particles. The shell material contains an adhesive resin as an essential component, and may further include a function imparting agent, a charge regulator, and other additives as optional components. (1) Binder resin As a binder resin for the shell material constituting the shell part of the microcapsule toner particles, the binder resin for fixing as described below can be used, and an olefin system having a ring structure is more desirable. polymer. The melting point and the softening temperature of the binder constituting the core material are resins having excellent storage stability. Examples of the fixing resin include derivatives of styrene or substituted styrene, derivatives of (meth) acrylic acid, (meth) acrylate, maleic anhydride or maleic anhydride ester, and maleic anhydride. Nitrogen-containing vinyl compounds such as amines, vinylpyridines, N-vinylimidazole, vinyl acetals, chlorinated olefins, acrylonitrile, 23- (20) (20) 200405141 vinyl monomers such as vinyl acetate, etc. Ethylene fork monomers such as vinyl chloride, vinylidene fluoride, etc. alone or copolymers of olefin monomers such as ethylene, propylene, etc., polyester, epoxy resin, polycarbonate, polyamide, polyurethane, polyurea, rosin, denatured Rosin 'phenol resin, melamine resin, polyphenylene ether, polyoxyphenylene and other condensation polymers' terpene resins, aliphatic or alicyclic hydrocarbon resins, petroleum resins, can be used alone or in combination of two or more of the above substances. In order to prevent the toner from being transferred to the offset image of the heat roller and further improve storage stability, an olefin-based polymer having the following cyclic structure is preferably used as a binder resin for the outer shell material. That is, the adhesive resin of the 'shell material is preferably a hydrocarbon storage polymer having an unmodified cyclic structure, but if the glass transition temperature is higher than 60. (:, The storage stability of toner can be sufficient. To ensure, it is also possible to replace the entire amount of the binder resin with an olefin polymer introduced with a carboxyl group, which has a carboxylic acid-modified cyclic structure. The olefin-based polymer having a structure having a number average molecular weight (Mn) of 1,000 or more and 100,000 or less, preferably 2,000 or more and 50,000 or less, and a weight average molecular weight (Mw) of 2,000 or more and 200,000 or less, It is preferably above 4,000, below 50,000, and the glass transition temperature (Tg) is above it: I 80 ° C or lower, preferably 60 ° C or higher, and 80 ° C or lower. On the other hand, The number-average molecular weight (Mη) of the olefin polymer having the carboxylic acid-modified cyclic structure is 1,000 or more, 100,000 or less, preferably 2,000 or more, and 50,000 or less, and the weight average molecular weight (Mw) is 3,000. Above, 300,000 or less, preferably 6,000 or more, 50000 or less, acid hydrazone is 5 to 50 (mg KOH / g), and glass transition temperature (T g) is 60 ° C Above, below 180 ° C, preferably above 60 ° C above 8 (TC. If the glass is turned -24- f * ύ (21) 200405141 If the temperature is lower than 60 ° C, the storage stability of toner particles will increase. On the other hand, if it exceeds 180 ° C ', the melting point will increase and the fixability tends to deteriorate. In addition, if the number average molecular weight is less than 1,000, sufficient fixing strength cannot be obtained. On the other hand, if it exceeds 100,000, it is not easy to ensure the necessary solubility in the solvent. In addition, if the acid hydrazone is less than 5, The improvement of the compatibility of the resin and the improvement of the adhesion to the paper are not good. If it is greater than 50, the color change becomes stronger, or the hygroscopicity is high and it is not practical.

Physical properties other than the glass transition temperature and number average molecular weight of olefin-based polymers having the above-mentioned cyclic structure, modified products, cross-linked products, etc., and those related to olefin-based polymers having the cyclic structure used in the above-mentioned core materials The description is the same. In addition, the introduction method of the carboxyl group of the olefin polymer having a carboxylic acid-modified cyclic structure, the type of the residual acid or carboxylic anhydride used for the modification, and the graft ratio are the same as those of the above-mentioned nuclear material. This description is omitted. (2) Function imparting agent

In order to expand the non-offset temperature range to further improve the non-offset property of the surface of the toner particles, the same material as the function imparting agent (wax, silicone oil) used in the above-mentioned nuclear material may be mixed in the shell material. The above-mentioned ideal use form and the like are also applicable to a function imparting agent mixed with a case material. (3) Charge adjuster The same material as the charge adjuster used in the core material may be mixed in the shell material. -25- (22) (22) 200405141 (4) External additives If necessary, the surface of the shell material of the microcapsule toner particles can be covered with external additives. The external additive is made of colloidal silica (including aerosol silica) and other fine powders of silica such as alumina, titanium oxide, and other liquids, or barium stearate, calcium stearate, and barium laurate. Lubricants made of metal salts can be used alone or in combination of two or more of them. In addition, it is preferable to use tritium hydration treatment separately. The amount of the external additive used is preferably 0.01 to 10 parts by weight, and preferably 0.05 to 5 parts by weight based on 100 parts by weight of the toner particles. To coat the shell material with an external additive, the solution containing the external additive can be applied to the surface of the particles, or attached to the surface by other methods. (5) Mixing amount of each component The mixing amount of each of the above components on the shell material is shown in Table 1 except for the colorant. [C] Microcapsule toner particles Microcapsule toner particles have a so-called core shell structure of a capsule type in which a core material is covered with a shell material. The particle diameter (diameter) of the whole particle is preferably 3 to 10 μm, and the periphery (outer diameter of the capsule—the diameter of the core material) x 1/2) is preferably 0.1 to 0.5 μm. In the present invention, there are three types of combinations of the core material and the shell material related to the binder resin: (a) Core material: an olefin polymer having a cyclic structure (-20 ° C STg 0-30 -26- (23) (23) 200405141 < 65 ° C? 100 < Mn < 20,000) > Shell material: fixing resin for fixing; (b) Core material: olefin-based polymer having a cyclic structure (_2〇tsTg & lt 65 ° C, 100 ^ Mη ^ 20,000) and a resin for heat fixing and / or pressure fixing resin. Shell material: olefin-based polymer with cyclic structure (60 ° c 180 ° C, 1,000 < Mη <100,000); (c) core material: olefin-based polymer with cyclic structure (-20 ° C < Tg < 65 ° C, 100 < Mn < 20,000), outer shell material: olefin-based polymer having a cyclic structure (60 ° C STgS 180 ° C, 1,000 < Mn < 1,100,000). It can be obtained as a result of a combination of various crystalline and amorphous resins in combination with a sintered hydrocarbon-based polymer having a cyclic structure, or exemplified as the above-mentioned fixing resins in [A] (l), which are relatively compatible with each other. Utilize the important toner properties of olefin polymers with cyclic structure-transparency, low temperature fixability, mechanical shock resistance and other characteristics. As the shell material, an olefin-based polymer having an acid-modified cyclic structure, a fixing resin described in [B] (1), or a mixture thereof may be used. In the form of the item (c) above, which uses an olefin polymer having a cyclic structure in both the outer shell material and the core material, the above-mentioned characteristics are fully utilized as the toner performance. Here, the best form of the toner particles is as follows: The core resin: ethylene, norbornene copolymer 'or copolymerized with carboxylic acid-27- (24) (24) 200405141, norbornene Substances (acid acid is about 10 mgKOH / g), the glass transition temperature (Tg) is 40 to 59 ° C, the number average molecular weight (Mη) is 1,000 to 10,000, and the weight average molecular weight (Mw) is 6,000 to 30,000, polydispersity (weight average molecular weight (Mη / number average molecular weight (Μη)) is less than 10, and the molar ratio of copolymerization of ethylene and norbornene is 85/15 to 95/5. Acid-modified ethylene, norbornene copolymer glass transition temperature (Tg) of 60 to 8 (TC, number average molecular weight (Μη) of 2,000 to 50,000, weight average molecular weight (Mw) of 6,000 to 200,000 »more The degree of dispersion (Mw / Mn) is 4 to 10, the molar ratio of the copolymerization of ethylene and norbornene is 75/25 to 85/15, the acid is about 10 mgKOH / g, and it is soluble in methyl ethyl [D] Manufacturing method of microcapsule toner particles The manufacturing method of the present invention is to make the above-mentioned Japanese Patent Application No. 10-3 1 22 1 5 The provided re-sinking method is further improved, and can produce uniform (-28) (25) (25) 200405141 (sharp) toner particles. That is, the manufacturing method of the present invention is characterized by color Agent and binding < Resin core material and electrostatic powder image developing toner formed by microcapsule toner particles composed of binder resin and microcapsule material composed of shell material for covering the core material, The core material solution in which the coloring agent is dispersed in the good solvent solution of the binder resin constituting the core material is sprayed and dropped into the weak solvent solution of the binder resin constituting the outer shell material as a droplet in the form of mist. (1) Examples of the method for spraying the droplets of the nuclear material solution into the shell material solution by the spray nozzle include a method using a spray nozzle and a method using a nozzle for an inkjet color printer. This type of nozzle can be a slightly spherical droplet with an estimated diameter of 2 to 50 microns. ① Nozzle for spraying The nozzle for spraying is to choose a commercially available insecticide or fungicide with a hole diameter of 2 to 50 μm, or the back Said The impact type fine mist nozzle is preferably 0.2 to 0.5 mm. Among various spray nozzles, the nozzles are installed with two spray holes having a diameter of about 0.4 mm and the spray direction is installed at nozzles forming an angle of about 120 degrees with each other. The impact type fine mist nozzle in the form of the impact of the jets is particularly desirable. The nozzle of this type is described in, for example, Japanese Patent Publication No. 4-9104. Figure 1 shows the appearance of the impact type fine mist nozzle. Fig. 2 is a partial cross-sectional view showing the shape of a spray hole at the tip of an impact type fine mist nozzle. In the first figure, two spray holes (11) are installed on the nozzle (1), and the intersection angle of the extension line of the liquid -29- (26) (26) 200405141 is 120 degrees. In FIG. 2, each ejection hole (11) has a double tube structure, and droplets are ejected from the inner tube (1 ia), and compressed air is ejected from the outer tube (lib). The droplets sprayed from the inner tube (iia) collided with the air sprayed from the outer tube (1 1 b) to form particles, and then the droplets that became the particles were sprayed from the spray holes on the other side. Further micronization and homogenization can become droplets with an estimated diameter of 2 to 50 μm. In addition, the air pressure applied around the nozzle is preferably 0.3 to 0.5 MPa. The nuclear material solution supplied to the nozzle is sucked and supplied from the suction tank. ② Nozzle for inkjet printer The nozzle for inkjet printer used in the present invention is accelerated by electrostatic means, and is biased to be emitted from the nozzle. The ink particles that make dot matrix type characters formed on paper, that is, the ink ejection nozzles commonly known as inkjet printers have the same structure. That is, in order to generate droplets of nuclear material, the nozzle has a means to generate high pressure in an instant, and responds to the pressure to splash the nuclear material droplets toward the shell solution. Regarding such nozzles, specifically, the droplet ejection method uses a piezoelectric element (piezo) volume change method, a multi-static electrostatic charge method, or a thermal element type volume change (the so-called Bubble Jet (registered trademark) Any one of the methods is ideal, especially the piezoelectric element (Piezo) type volume change method is ideal. In addition, the shape of the nozzle is from several to 50 holes, each hole is 10 to 30um is ideal In addition, although the diameter of the nozzle is so large, the estimated diameter of the droplets to be ejected is 5 to 50 μm. • 30- (27) (27) 200405141 (3) Solvent ① The solvent of the nuclear material constitutes the A good solvent for the binder resin, that is, a binder resin included in the core material, such as an example of a solvent that can be mixed with an olefin polymer (such as an ethylene-norbornene copolymer) having an unmodified cyclic structure without restriction. There are benzene, toluene 'xylene, or cyclohexane. When using an inkjet nozzle, the solvent is protected from the viewpoint of protecting the nozzle member. The aromatic solvent is not ideal, and it is compatible with aliphatic hydrocarbons and alicyclics. Hydrocarbon mixture A naphthenic solvent is ideal. Such a naphthenic solvent is a C6 to C9 alkane, and the naphthenic component is, for example, sold by Exxon Chemical Co., Ltd. under the trade name of "Exeter" and is divided into Exeter DSP 100/140, D30, D40, D8Q, D110 grades, the composition of the components is different from each other. The boiling point is 50% of normal pressure, 120 to 18 (TC. To use carboxylic acid-modified olefin-based olefin polymerization In the case of methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), the concentration of the binder resin in the solution is adjusted to make spherical particles with the optimal particle size. 5 to 30% by weight is appropriate to adjust the viscosity of the solution. ② The solvent of the shell material constitutes the weak solvent of the binder resin of the shell material, that is, although it has the ability to dissolve the binder resin contained in the shell material, the solubility is Examples of limit solvents are MEK, MIBK, and Exeter. To use an olefin-based polymer with an unmodified cyclic structure, use a green hydrocarbon polymerization that does not easily dissolve in a carboxylic acid-modified structure with a nuclear component. -31-(28) (28) 200405141 Kessel and other naphthenic solvents. The concentration of the binder resin in such a solution is appropriate to adhere to the periphery of the nuclear material, and is preferably set to 1 to 5% by weight. ③ Specific manufacturing examples use the present invention The manufacturing method (solvent reprecipitation method) of toner particles for a spray nozzle is specifically described below. 20 to 35% by weight of an olefin polymer having a cyclic structure constituting a core material and 2 to 3.5% by weight of a function-imparting agent. Add 61.5 to 78% by weight of a solvent such as toluene at 25 to 30 ° C to dissolve it, and prepare a solution (disperse 1 to 2% by weight) of a disperse colorant with a ball mill (BEADS MILL). . On the other hand, about 98% by weight are dissolved in a solvent such as methyl ethyl ketone (MEK) in an amount of 1.8 to 2.2% by weight of an olefin polymer having a cyclic structure constituting the outer shell material and 0.01 to 0.025% by weight of a charge modifier. % To prepare a solution (B liquid). Then, the liquid flow path with an outlet hole diameter of 0.45 mm as shown in Figures 1 and 2 and the two nozzles with a structure having an air flow path around it mix the A liquid with air into a mist, and at high speed Sprayed into a porcelain plate (vat) containing liquid B under stirring to obtain a precipitate. At this time, the scattered mist is drawn by the exhaust pump and recovered in the B liquid trap. Then, put it into the filter 俾 to separate it from the solvent, and finally, distill the residual solvent into pellets with a high-temperature vacuum dryer. In this way, it can be made and slightly spherical in shape, with an average particle size of 4 to 10 um, a particle size distribution of 2 to 12 m, σ = equivalent to 3 (7) from time to time with standard deviation, and a shell material thickness of 0.2 to 0 • 5 μm (measured according to the weight of the solvent separation method) microcapsule toner particles. The other is used as a developer, and additional. 疎 water-based silica is added. In addition, the manufacturing method of toner particles using nozzles for inkjet printers -32- (29) (29) 200405141 is also permitted. [Embodiment] The present invention will be described more specifically with reference to examples and comparative examples below. The toners of the dry unit system and the dry two-component system are prepared as described below. In addition, Examples 1 and 3 are examples of manufacturing microcapsule toner using a spray nozzle, and Examples 2 and 4 are examples of manufacturing microcapsule toner using a nozzle for an ink jet printer. [Example 1] (Using a spray nozzle) ① Preparation of the resin body A was mixed and kneaded by biaxial extrusion. An olefin polymer having a ring structure had a glass transition temperature (Tg) of about 65 ° C and a weight With an average molecular weight (Mw) of about 9,000, 93% by weight of "Dorbus TM" (trade name) manufactured by Ticona Corporation, and 2% by weight of Yamagata Soda Ammonium Wax ("BTN22H" manufactured by Nippon Seika Corporation). , Fine powder of a mixture of non-oxidized polyethylene waxes (2% by weight of Celeste 371 5F (trade name) manufactured by Clariant Co., Ltd., and a cyan colorant ("Cyanide BG" manufactured by Clariant Co., Ltd.) 3% by weight of the resin precursor A. ② Preparation of liquid A (nuclear material) in 75% by weight of toluene, at a temperature of 30t, and slowly adding 25% by weight of the above resin precursor A to dissolve it. Then, disperse the resin portion of the solution with an ultrasonic cleaner, and then stir with a stirrer at a stirring speed of 9,500 rpm to obtain a solution. Next, use a 200 mesh-33- (30) (30) 200405141

(mesh) The solution was filtered under pressure and foreign matter was removed. The viscosity of this liquid A measured by a type B viscometer was 17.8 cp (centipoise). (No. 1 rotor, 60 rpm, 20 ° C) ° ③ The resin body B was prepared by mixing the olefin polymer with a ring structure with the same biaxial extruder as above, and the glass transition temperature (Tg) was 65 ° C, the weight average molecular weight (Mw) is 50,000, the maleic anhydride 5% grafted into the product (Tg) by Tecna is 65 ° C, the Mw is about 50,000, and the acid is about 50,000. It is made of 10 mg KOH / g of 98% by weight of "Dibus BG" manufactured by Tecna and 2% by weight of the charge modifier ("E-84" (trade name) manufactured by Far Eastern Chemical Co., Ltd.). Granule process: 1. Using the impact type fine mist nozzle ("AKIJET" manufactured by Ichiuchi Co., Ltd.), the A liquid is sprayed onto the B liquid at a pressure of 0.3 to 0.5 MPa and dropped. Meanwhile, the B liquid was stirred at a speed of 300 rpm by a stirrer. The dropping time was about 3 minutes until no funnel remained in the funnel and a precipitate was obtained. After dripping, stirring was continued for 5 minutes as it was. A funnel made of Teflon (registered trademark) is installed on the top, and the scattered toner particles are attracted by a vacuum pump installed at its tip. The dripped liquid B was absorbed and filtered with a filter paper capable of maintaining 3 μm. In the liquid B to be filtered, a small amount of ethanol was added to replace the solution. Finally, the solution was washed with ethanol and filtered. Microcapsule toner particles were obtained by distilling the residual solvent of the filter substance with a high vacuum dryer. The average particle size of the toner particles produced by Lai-34- (31) (31) 200405141 was about 7 μηι, and it was found that All particles have a particle size distribution in the range of 3.5 to 11 μm, and have uniform particles that do not need to be classified as coarse and fine particles, so they have excellent productivity. In addition, the shape of the toner particles was observed by a scanning electron microscope to confirm that they were slightly spherical. The average particle size of the toner particles is a number 値 obtained by using a laser refraction scattering particle size distribution measuring device ("LA-700" manufactured by Horiba, Ltd.). In addition, the particle size distribution is measured by the same device. The particle size of 3 to 9 μm exceeds 90% of the volume basis, and the particle size of 2.3 to 9 μm is about 95%. In addition, the thickness of the shell material is measured by measuring 10 g of toner particles in 1 liter of methyl ethyl ketone, heating to 50 ° C and stirring for 20 minutes to dissolve the shell material, and then hot filtering to distill off the solvent. Measure the residual weight to calculate it. [Example 2] (Using a nozzle for an inkjet printer) ① The preparation of the resin body A was the same as that of the above-mentioned Example 1. ② Preparation of liquid A Exxon D-30 or D-40 using naphthenic solvents because of the consideration of viscosity and surface tension. Using these solvents, the solution was prepared as a liquid A (nuclear material) solution to a polymer concentration of 15 to 20%. After the preparation, the resin component in the solution was dispersed with an ultrasonic cleaner, and then stirred at a speed of 9,500 rpm with a stirrer. Then, pressure filtration was performed using a filter paper with a 10 μm pore size to remove foreign matter. Then degassing was performed to remove the dissolved air. For inkjet printers, about 20 nozzles with a 15pm aperture are used. ... 35- (32) (32) 200405141 ③ The preparation of the resin body B is the same as that of the first embodiment. ④ The preparation of the B liquid (shell material) is the same as that in the first embodiment. ⑤ Granulation project. After the nozzle A (piezo element volume change method) of the inkjet printer was filled with the liquid A, the liquid was sprayed in the liquid B stirred at 300 rpm for about 20 minutes. After spraying, the B liquid containing particles was absorbed and filtered by a filter paper capable of maintaining 3 μm. During filtration, the B liquid in a Biichner funnel was slowly stirred with a stirring blade to filter. During the filtration, liquid replacement was performed while adding a small amount of ethanol, and finally, washing with ethanol and filtration were performed. Micro-capsule toner is produced by distilling the residual solvent in the filter with a high vacuum dryer. After confirming the particle diameter with an electron microscope, the average particle diameter of the produced toner particles was about 7 to 8 μm, and the particle size distribution was 3 to 15 μm. [Example 3] (Using a nozzle for spraying) ① Preparation of resin precursor A A olefin polymer having a cyclic structure was kneaded with a biaxial extruder with a glass transition temperature (£) of 65 ° 0 and a weight average molecular weight ("~") Is 5% maleic acid of "Dose TB" manufactured by Dicana, and the Tg of the grafted finished product is 65 ° C, the Mw is about 50,000, and the acid content is about 10 mgK. H / g, 93% by weight of "Dorken Bus TBG" manufactured by Ticona Company, and the function imparting agent is benzamine wax (2% by weight of "BNT22H" manufactured by Nippon Seika Co., Ltd.), an oxidized and non-oxidized polyethylene wax Fine powder of the mixture ("Aliast · 36- (33) (33) 200405141 3715F" (trade name) manufactured by Clariant Co., Ltd.) (trade name) 2% by weight and a cyan coloring agent ("Pink Cyanide manufactured by Clariant Co., Ltd." BG ") 3% by weight to obtain the original resin body A. ② A solution (nuclear material) was prepared in 80% by weight of methyl ethyl ketone and stirred at 200 rpm at a temperature of 30 ° C. Slowly add 20 parts by weight of the above-mentioned resin precursor A to dissolve it. Then, disperse the solution in an ultrasonic washer. The resin component was then stirred with a stirrer at a stirring speed of 9,500 rpm to obtain a solution. Then, the solution was filtered under 200 mesh pressure to remove foreign matter. The viscosity of the A liquid was 35.5 cp (centipoise) measured with a B-type viscometer. ) (No. 1 rotor, 60i.pm, 20 ° C). ③ Modulation of the resin body B. The olefin polymer with a ring structure is kneaded with a biaxial extruder. The glass transition temperature (Tg) is about 65 ° C. , With a weight average molecular weight (Mw) of about 50,000, 98% by weight of "Dobas TB" (trade name) manufactured by Dicana, and 2 weights of a charge modifier ("E-84" (trade name) manufactured by Tohoku Kasei Corporation) % Resin precursor B. ④ Preparation of B liquid (housing material) 5% by weight of the above resin precursor B was dissolved in 95% by weight of EXX〇1 D — 3 0 (trade name) D — 3 0 and Liquid B was obtained. ⑤ The granulation process was performed in the same manner as in Example 1. The average particle size of the produced toner particles was about 8.5pm, and the particle size distribution was that all particles were concentrated in the range of 4.5 to 15 μm, and because The uniformity of the series without having to distinguish between coarse and fine particles Further, the shape of the toner particles is confirmed via a ball slightly observed with a scanning electron microscope of

-37- (34) (34) 200405141. In addition, the average particle diameter of the toner particles and the thickness of the casing material were also measured or calculated in the same manner as in Example 1. [Example 4] (Using a nozzle for an inkjet printer) ① The preparation of the resin body A was the same as that of the above-mentioned Example 3. ② Preparation of A liquid (nuclear material). As the solvent, methyl ethyl ketone was used. The solvent was used to prepare the solution so that the liquid A solution had a polymer concentration of 15 to 20%. After the preparation, the resin component in the solution was dispersed with an ultrasonic washing machine, and then stirred at a speed of 9,50 (hpm) with a stirrer. Then, the filter was filtered using a filter paper with a diameter of 10 μm to remove foreign matter. Then defoaming was performed. In order to remove the dissolved air. About 20 nozzles with a 15 μm aperture are used for inkjet printers. ③ The preparation of the resin body B is the same as that of the above embodiment 3. ④ The preparation of the B liquid (housing material) and The above Example 3 is the same. ⑤ Granulation process. The method is the same as in Example 2. The average particle size of the produced toner particles is about 7 to 9 μm, and its particle size distribution is 3 to 20 μm. [Comparative Example 1] "Example 1" of JP 2000-1 47829) ① Preparation of A liquid (nuclear material solution) An olefin polymer having a cyclic structure is prepared by using a glass transition temperature (Tg) of 49 ° C and a number average molecular weight (Mη ) Is a 2,000-unit "Dicolor-38- (35) (35) 200405141 Shi T — 936" manufactured by Ticona, Inc., an olefin polymer having a cyclic structure modified with acrylic acid. The glass transition temperature is used. (Tg) is 58 ° C, the number average molecular weight (Μη ) Is 1% by weight of "Dorex AG — 07" manufactured by Dikon Company of 3,700, and the functional imparting agent is 0.5% by weight of "BNTT 22Η" manufactured by Nippon Seika Co., Ltd. and "Ceridust 3715" (commodity manufactured by Clariant Co., Ltd.) Name) 0.5% by weight 'Placed in 80% by weight toluene, cyclohexane mixed solvent (weight ratio 50 to 50)' at 3 (TC temperature, slowly increase and dissolve at a stirring speed of 20 (kpm). Then, to this solution, beads (stainless steel powder manufactured by Lusong Co., Ltd .; particle size of 500 μm) were added, and a black coloring agent ("Carbob Black MA-7" manufactured by Mitsubishi Chemical Corporation) was slowly added to the solution, and Liquid A is prepared by dispersing at 500 rpm. ② Preparation of liquid B (housing material) The olefin polymer having a ring structure has a glass transition temperature (Tg) of 67 ° C and a number average molecular weight (Μη) of 4,600. 2% by weight of "Kona Bus AG-09" manufactured by Kana Corporation and a charge modifier ("Copy Charge NX" (trade name) manufactured by Clariant Co., Ltd., 0.02% by weight) are dissolved in about 98% by weight of methyl ethyl ketone. Preparation and B liquid. ③ Granulation process has more The nozzle with a hole with a diameter of 30um drips the above-mentioned liquid A into liquid B under high-speed stirring to produce particles. At this time, the particle size of the liquid a that is dropped is estimated to be 20 to 40 μm. When manufactured in a 500-liter capacity pot, the drops The injection volume is 200 liters of liquid B, which is made from 100 pieces of orifice at a rate of 5 liters per minute and slowly dripped into 100 liters of liquid A for 20 minutes. The stirring speed was 2,000 rpm. After the droplet A was completely dripped, the stirring was continued for 10 minutes. Then, the -39- (36) (36) 200405141 precipitate was put into a filter to separate it from the solvent, and the residual solvent was removed with a high-humidity vacuum dryer to remove the residual solvent to obtain microcapsule toner particles. The average particle size of the obtained toner particles is about 1 nm, and its particle size distribution is in the range of 3 to 15pm. Further, as a result of observation with a scanning-type electron microscope, it was confirmed that the shape was slightly spherical. [Comparative Example 2] A toner produced by a commercially available air impact pulverization method (so-called jet pulverization method) has an average particle diameter of 7.0 μm and a particle size distribution of 1.8 to i7jJm. [Comparative Example 3] is The toner produced by the mechanical crushing method on the market is specifically a toner for a printer "Magicol 2-2CX" (trade name) manufactured by QMS. [Evaluation of manufactured toners] The microcapsule toners manufactured in the above Examples 1 to 4 and the toners of Comparative Examples 1 to 3 were used in a Ricoh photocopier "FT-55 20" to perform the performance described below Quiz and assessment. The results are shown in Table 2. (a) Waste toner resistance Use the toner samples of each of the examples and comparative examples to perform a copy test on high-quality paper until the toner components adhere to the sleeve and the photoreceptor to a tolerance of -40-

A Λ A (37) (37) 200405141 limit, and compare the number of ordinary paper. (B) Reproducibility · 'The efficiency of copying the photoreceptor onto the high-quality paper of the base material after photocopying 10, 000 sheets, based on the amount of recovered toner. (C) Fixability Use various toners to form an image on high-quality paper, cover it with the same quality paper with no image printed on it, and wipe the image with a friction tester to force it to be copied onto the unprinted paper . The image formation speed was 150 mm / sec, and the fixing temperature was 150 ° C. The conditions for the friction test were 20 back and forth with a load of 2 pounds (about 907 grams). After rubbing, the initial image density (A) before the rubbing, the copy density (B) of the unprinted paper, and the density (C) of the non-image parts of the paper were measured with a Markbeth reflection thermometer, and the use of The formula [(B — C) / A x 100 (%)] measures the replication ratio. Measurements showed that the fixed image lower limit temperature and the fixed image lower limit pressure of the reproduction ratio exceeded 60% for comparison. (d) Image quality The color properties, fine line resolution, and OHP transparency are compared and evaluated for each toner image (sex). ① Tonality: It is evaluated based on the number of gray scale identification steps of 0 to 16 for the image samples made by Quest. ② Fine line resolution: -41-(38) (38) 200405141 According to the data, the fine line image of the image sample made by Quest is evaluated from 0 to 600dpi. ③ OHP transmittance An image is formed on an OHP film for PPC manufactured by Fuji Quanlu Co., Ltd. to measure the amount of light transmitted through the image portion (A) and the non-image portion (B), and a / BX 1 0 0 (° / 〇). (e) Storage stability After the toners adjusted by each formula are stored under the conditions of 60 ° C and 50% RH (relative humidity) for 8 hours, the residual amount of screening when the mesh is screened for a certain period of time is divided by It is expressed as a percentage after using the sample amount. If the toner particles agglomerate during storage, the number will increase. The main reason is caused by the low melting point of 50 C to F contained in the toner composition. When the screening residual amount is less than 0.5%, the symbol 0 is attached, and when it exceeds 0.5%, the symbol X is attached. 42- (39) 200405141 Table 2

Evaluation item Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Waste toner resistance (number of pieces) 75,000 80,000 70,000 75,000 50,000 20,000 20,000 Reproducibility (%) 100 100 100 100 99.8 95.0 99.0 Fixing lower limit pressure (kg / cm2) 10 10 10 10 50 450 330 Lower limit temperature rc) 80 80 80 80 100 140 130 Graphical hue 16 32 16 32 16 8 8 Fine line resolution (dpi) 600 1200 600 1200 600 300 300 〇HP penetration 95 98 92 95 95 90 92 Storage stability 〇〇〇〇〇XX

[Industrial Applicability] Since the present invention has the following excellent effects, it has industrial applicability. By using the manufacturing method of the microcapsule toner of the present invention, that is, the method of using a spray nozzle or a nozzle for an inkjet printer when spraying a nuclear material solution on a shell solution, a microcapsule with uniform particle size distribution can be produced. Capsule toner, and the prepared toner has good storage stability, will produce a sharp and high-level image, and is superior in waste toner resistance, reproducibility, fixability and non-offset. In particular, even under a low-temperature heating method, it has excellent fixability and is excellent in appearance. In addition, in the heat roller fixing method, it is easy to greatly reduce the heat, which can contribute to the energy saving of the d4f -43- (40) (40) 200405141 machine. In addition, if the shell material contains a function imparting agent such as silicone oil or wax, it is not necessary to apply oil to the surface of the heat roller. When using nozzles for inkjet printers, because the components of the nozzles are easily attacked by aromatic solvents, the solvents of the nuclear material solution can be aliphatic, cycloaliphatic solvents of alicyclic hydroxyl compounds in response to pressure. Copying machine for heating fixability. [Brief description of the drawings] Fig. 1 is an external view of an impact type fine mist nozzle. Fig. 2 is a partial cross-sectional view showing the shape of a spray hole at the tip of an impact type fine mist nozzle. • I · • * ·· [Comparison of main components] I Impact type fine mist nozzle II Impact hole of tip of fine mist nozzle 11 a Inner tube of spray hole 11 b Outer tube of spray hole Θ'4Α 44-

Claims (1)

(1) (1) 200405141 Patent application scope 1 · A manufacturing method of toner for electrostatic charge image development, which is manufacturing of toner composed of microcapsule toner particles composed of nuclear material and shell material In the method, the core material is formed of an adhesive resin containing an olefin-based copolymer having a colorant and a cyclic structure, and the shell material is composed of an adhesive resin to cover the core material. The fine solvent solution of the binder resin of the core material is sprayed with particulate droplets of the core material solution in which the colorant is dispersed, and is dripped into the weak solvent solution of the binder resin constituting the shell material to be encapsulated. 2. The method for manufacturing a toner according to item 1 of the scope of patent application, wherein the fine particles of the nuclear material solution are sprayed and sprayed into the solution of the shell material by using a spray nozzle. 3. The manufacturing method of toner according to item 1 of the scope of patent application, wherein the droplets of the core material solution are sprayed and dropped into the solution of the shell material by using a nozzle of an inkjet printer. 4. The manufacturing method of toner according to item 3 of the patent application, wherein the method of using the nozzle of the inkjet printer to spray the particulate droplets of the nuclear material solution into the solution of the casing material is a piezoelectric element type volume Either the electric field control of the change and multi-static electrostatic charge method and the thermal element volume change are selected. 5. The method for manufacturing a toner according to item 3 of the patent application, wherein the solvent of the nuclear material solution is a naphthenic solvent of a mixture of an aliphatic hydrocarbon and an alicyclic hydroxyl. 6. The manufacturing method of toner according to item 1 of the scope of patent application, wherein the binding resin constituting the core material is made of a glass transition temperature of -2 (TC above 65 ° C and below) and a weight average molecular weight of 200 or more and 40,000. The following range is -45- (2) (2) 200405141 cyclic structure of olefin-based copolymers. 7. The manufacturing method of toner according to item 1 of the patent application scope, wherein the core material has a cyclic structure The olefin-based copolymer resin is a copolymer modified by a carboxylic acid or a carboxylic anhydride. 8. The manufacturing method of the toner according to item 1 of the patent application scope, wherein the adhesive resin constituting the outer shell material is made of a glass transition temperature. 60 ° C to 1 80 ° C, and a cyclic olefin copolymer with a weight average molecular weight of 2,000 to 200,000. 9. As described in the patent application, the toner of item 1 A manufacturing method in which an olefin-based copolymer resin having a cyclic structure constituting a shell material is a copolymer modified by a carboxylic acid or a carboxylic anhydride. 1 ·· The manufacturing method of the toner according to item 1 of the patent application scope, wherein For the adhesive resin constituting the core material and / or the adhesive resin constituting the outer shell material, a wax is used. 11. For a method for producing a toner according to item 1 of the patent application scope, in which rhenium is composed of fatty acid tar wax, At least one selected from the group consisting of a mixture of oxidized polyethylene wax, acid-modified polypropylene wax, and oxidized and non-oxidized polyethylene flame. 12 · —A kind of toner for electrostatic charge imaging development, characterized in that: Those who apply or apply fine powder to the surface of the microcapsule toner particles produced by the toner production method described in the first item of the patent scope.