WO2004025374A1

WO2004025374A1 - Process for producing toner for electrostatic image development

Info

Publication number: WO2004025374A1
Application number: PCT/JP2003/010942
Authority: WO
Inventors: Toru Nakamura; Hisakazu Ikebe; Shinsuke Fujioka
Original assignee: Ticona Gmbh
Priority date: 2002-09-12
Filing date: 2003-08-28
Publication date: 2004-03-25
Also published as: JP2006023322A; TW200405141A

Abstract

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 are 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

Description Method of manufacturing toner for developing electrostatic images

Technical field

The present invention relates to a method for producing a toner for developing an electrostatic image of a pressure fixing type and a heating roller fixing type (hereinafter sometimes referred to as a “pressure heating type” or a “pressure heating type”).

More specifically, the present invention relates to a method of fixing a dry magnetic one-component system, a dry non-magnetic one-component system, a dry two-component system, a liquid dry system, and a liquid toner-based developer to a substrate to be copied such as paper or film. Sufficient fixability, toner spent property, transparency, and clear images that enable pressure fusing and enable pressure fusing at a low temperature of less than 100 ° C even in the case of hot roll fusing. The present invention relates to a method for producing a toner capable of forming a toner. Further, the present invention relates to a method for producing a toner in a developer which can be practically used, which is excellent in high-speed settability and storage stability in which a temperature range in which an offset phenomenon does not occur (non-offset temperature range) is excellent. It is about.

Further, the present invention relates to the toner which can be widely applied to a copying machine, a printer, a facsimile, a color copying machine, a color laser copying machine, a color laser printer, and an electrophotographic high-speed printing machine. Background art

With the rapid spread of office automation, improved mechanical shock resistance for high-speed printing speed in electrostatic image developing type copiers and printers, high quality, vivid image quality, low-temperature fixability, color toner support There is an increasing demand for copied images that have excellent light transmission properties. To meet the demands for such high-speed copying and high-quality images, the required and sufficient toner particle mechanical strength, a wide non-offset temperature range that can sufficiently meet the requirements for low-temperature fixing, and the fixing roll are required. Oil-freeter that does not require oil supply and does not contaminate the substrate to be copied Eve is expected to be realized.

Toners have a wide range of performance requirements, including chargeability, fixing properties, abrasion resistance, transportability, and storage stability (the toner particles are less likely to aggregate and form a block even after a long period of time). Therefore, there is a limit to satisfying all needs when they are dry-mixed by the conventional compound method.

In other words, in order to meet each of the above needs, it is necessary to add various contradictory functions to the toner. To solve such problems, core material (nuclear material) particles called cores A micro-forced Psertona has been devised in which the shell is covered and wrapped with a shell material (shell material) called a shell. According to the Microforce Pusseltoner method, for example, a binder resin that has good fixability but is poor in storage stability and easily causes an offset phenomenon is used as a core material, while storage stability and non-offset properties are good. This is because the conflicting demands can be solved by using the resin for the outer shell. There have been many inventions and ideas relating to such a function-separated type microcapsule toner.

For example, Japanese Patent Application Laid-Open No. 9-292735 discloses a film fixing and heating type image forming apparatus using a microcapsule capsule toner manufactured by a suspension polymerization method, and an example using the same manufacturing method is disclosed in It is disclosed in Japanese Unexamined Patent Publication No. 59-53856 and Japanese Patent Laid-Open No. 59-61842.

Japanese Patent Publication No. 56-13945 discloses a method for producing a toner by a spray-dry method, and Japanese Patent Publication No. 8-169793 discloses a method for producing a microcapsule toner by a water-dropping phase separation method. Japanese Patent Application Laid-Open No. 3-56970 proposes a method for producing a micro-capsule toner which forms a shell layer by in-situ polymerization and then forms fine particles using a high-pressure homogenizer. . In addition, an interfacial polymerization method, a coacervation method, a dry force pressel method, and the like are introduced.

Japanese Patent Application Laid-Open No. 10-10778 discloses a method for producing a toner having a self-water-dispersible resin, a solvent, and a colorant by phase inversion emulsification in an aqueous medium for the purpose of improving charging. Have been. A method for producing a capsule toner by the force and phase inversion emulsification method is disclosed in JP-A-11-65168, JP-A-10-2071119 and JP-A-10-207119. It is also disclosed in JP-A-11-231569.

In JP-A-10-78676, an amorphous polyester having an acid value of 9.5 (mgKOH / g) is used as a resin for the outer shell of a forcepsel to improve blocking resistance. In Japanese Patent Application Laid-Open No. 10-228130, the low-temperature fixability and the anti-offset property are improved by defining the storage activity of the force-sensitive toner produced by the in-situ polymerization method. JP-A-10-301328 describes that a toner for developing an electrostatic image having a capsule structure having a specific amount of a resin component soluble in a mixed solvent provides low-temperature fixability and high image quality. Japanese Patent Application Laid-Open No. 2000-98510 proposes a method for producing a low fixing temperature toner having a low fixing temperature by polymerizing a polymerizable monomer composition containing a colorant in an aqueous dispersion medium. It states that force capsules whose shell is made of an _ε- force prolactone ring-opening polymer have excellent low fixing temperature.

JP-A-2000-112175 and JP-A-2000-112176 propose a method of producing a capsule toner having excellent fixing characteristics by dissolving a binder resin in a dispersion of powdered toner particles.

In addition, Japanese Patent Application Laid-Open No. 11-305478 and Japanese Patent Application Laid-Open No. 2000-284525 have proposed capsule toners for the purpose of improving low-temperature fixability and storage stability.

However, these conventional methods for producing toners, except for the spray drying method, all use water as a medium, so that drying is troublesome, and it is still not enough to produce microcapsule toner on an industrial scale. It was actual. In addition, it was difficult for the spray-drying method to produce fine particles to obtain a desired average particle size, usually 10 μηι or less.

Under these circumstances, the present inventors have disclosed in Japanese Patent Application No. 10-312215 (Japanese Patent Application Laid-Open No. 2000-147829) that the binder resin has a glass transition temperature of not less than 120 ° C. and less than 60 ° C. The core material contains an olefin copolymer having a cyclic structure with a number average molecular weight in the range of 100 to 20,000 and a glass transition temperature of 60 to 180 ° C as Z or a binder resin. Number average molecular weight in the range of The invention relating to a toner for developing an electrostatic charge image having microcapsule toner particles containing an olefin copolymer having a cyclic structure having a cyclic structure of not less than 1,000 and not more than 100,000 is not described above. It has been disclosed that it can respond to requests.

However, the method for producing a microcapsule toner disclosed in the above invention is an ordinary reprecipitation method, that is, a nucleus in which a colorant is dispersed in a good solvent solution of a binder resin constituting a nucleus material. A solvent re-precipitation method in which a material solution is dropped into a poor solvent solution of a binder resin constituting the outer shell material to precipitate the outer shell material around the core material, or a phase separation method. In the toner obtained in the above, it is insufficient to suppress the variation of the particle diameter within a predetermined range, and it is not possible to sufficiently meet the demand for supplying a toner having a sharp particle diameter distribution on an industrial scale. The problem that was left.

Disclosure of the invention

An object of the present invention is to sufficiently cope with a low-temperature heat fixing method or a pressure fixing method for realizing high-speed copying and a heating roller fixing method, and to solve the problems of the conventional micro-pressurized toner. An object of the present invention is to provide a method for producing a microcapsule toner having a uniform particle size distribution, which is excellent in stability and prevention of an offset phenomenon, and can exhibit a high density hue.

The present inventors have formulated two types of olefin polymers having a cyclic structure having different glass transition temperatures and number average molecular weights as a binder resin constituting a core material and / or an outer shell material of microcapsule toner particles. When the core material solution is dropped into the outer shell solution in the production of the electrostatic charge image developing toner, the core material solution is sprayed as fine droplets into the outer shell material solution to be encapsulated. As a result, they have found that the above-mentioned problems can be solved, and have completed the present invention.

That is, the present invention provides a microcapsule toner comprising: a core material made of a binder resin containing a colorant and an olefin-based copolymer having a cyclic structure; and an outer shell material made of the binder resin and covering the core material. Of toner for electrostatic image development composed of particles In the above, fine droplets of the core material solution in which the colorant is dispersed in the good solvent solution of the binder resin constituting the core material are jetted into the poor solvent solution of the binder resin constituting the outer shell material, The present invention relates to a method for producing a toner for developing an electrostatic image, which is characterized in that the toner is dropped and encapsulated. The present invention also relates to the above-mentioned method for producing a toner, wherein fine particles of a nucleus material solution are jetted and dropped into an outer shell material solution using a spray nozzle or a nozzle for an ink jet printer.

Furthermore, the method of jetting a nuclear material solution using a nozzle for an ink jet printer is one of a piezoelectric element type volume change, a multi-value electrostatic charge type electric field control, and a thermal element type volume change. thing ;

When a nozzle for an ink jet printer is used, the solvent of the core material solution is a naphthenic solvent which is a mixture of an aliphatic hydrocarbon and an alicyclic hydrocarbon;

The binder resin constituting the core material has a cyclic structure in which the glass transition temperature is in the range of 20 ° C to 65 ° C and the weight average molecular weight is in the range of 200 to 40,000. Having an olefinic copolymer having;

The olefin copolymer resin having a cyclic structure constituting the core material is a copolymer modified with carboxylic acid or carboxylic anhydride, preferably atrialic acid or maleic anhydride;

The binder resin constituting the outer shell material has a glass transition temperature of 60 ° C or more and 180 ° C or less and a weight average molecular weight of 2,000 or more and 200,000 or less. The olefin copolymer having a cyclic structure, which constitutes the outer shell material, is composed of a carboxylic acid or a carboxylic anhydride, preferably atrialic acid or maleic anhydride. Being a modified copolymer;

Use a binder resin that constitutes a core material and Z or a binder resin that constitutes an outer shell material mixed with wax;

The wax is a mixture of fatty acid amide wax, oxidized polyethylene wax and acid-modified polypropylene wax and oxidized and non-oxidized polyethylene wax. At least one member selected from the group consisting of

The present invention also relates to a toner for developing an electrostatic charge image, characterized in that silica fine powder is externally added or applied to the surface of the microcapsule toner particles produced by the above-mentioned method for producing a toner. Hereinafter, the present invention will be described in detail.

[A] Materials that make up the core material of microcapsule toner particles

The core material includes a binder resin and a colorant as essential components, and may further include a function-imparting agent, a charge control agent, and other additives as optional components. .

(1) Binder resin

The core resin of the microcapsule toner together with the colorant, that is, the olefin polymer having a cyclic structure or the olefin polymer having a cyclic structure as a binder resin constituting the nucleus material, and a heat fixing binder described below. A mixture with a resin and / or a binder resin for pressure fixing is used. These are resins having a lower melting point or softening point and higher fixability than the binder resin constituting the outer shell material described later.

Examples of the heat fixing binder resin include styrene-based polymers such as polystyrene and substituted polystyrene, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, and styrene-acrylic acid-tolyl copolymer. Examples include styrene-based polymers, atalylic acid-based resins such as poly (meth) acrylic acid resins and poly (meth) acrylate resins, polyester resins, and epoxy resins. These may be used alone or in combination of two or more. I can do it.

On the other hand, the binder resins for pressure fixing include plant, animal, mineral, and petroleum-based resins (specifically, carnauba wax, candelilla wax, lanolin, honey, montan wax, paraffin wax, microcrystalline Waxes), higher fatty acid derivatives (eg, stearic acid, palmitic acid, oleic acid, lauric acid and other polyhydric alcohol esters and higher grades such as calcium stearate, zinc stearate, lead stearate, magnesium stearate, etc.) Fatty acid metal salts, etc.), polyolefin wax (eg, polyethylene wax, polypropylene) Olefin-based homo- or copolymers (for example, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic ester copolymer, ethylene-vinyl acetate copolymer, ionomer resin, etc.) Styrene resins (for example, low molecular weight polystyrene, styrene-butadiene copolymer, styrene-acrylo-tolyl copolymer, etc.), epoxy resins and polyester resins. These may be used alone or in combination of two or more. It can be used in combination.

In order to enable high-speed copying by introducing a low-temperature fixing method and obtain high-quality and clear images, it is necessary to ensure reliable fixing properties compatible with the pressure heating fixing (thermocompression bonding) method. It is necessary to appropriately select the type and composition of the binder resin depending on the method. From the viewpoint of enhancing the non-offset property by expanding the non-offset temperature range where the offset phenomenon does not occur, the following olefin polymer (Cyclo Olefin Copolymer: COC) having a cyclic structure is used as the binder resin for the core material. Is preferred. The olefin polymer having a cyclic structure used as a core material has a higher number of molecular weights (Tg) in the range of -20 ° C to 65 ° C in order to obtain a higher degree of fixing property than the outer shell material. Mn) must be in the range of 100 to 20,000. If the glass transition temperature is lower than 120 ° C, the viscoelasticity increases and the printed image becomes sticky. On the other hand, if the glass transition temperature exceeds 65 ° C, the printed image is too rigid to obtain sufficient fixability. On the other hand, if the number average molecular weight is less than 100, sufficient fixability cannot be obtained. On the other hand, if the number average molecular weight exceeds 20,000, it is difficult to dissolve in a solvent, which is a serious problem in practical use.

Here, the glass transition temperature (T g) is the temperature at the midpoint of the displacement that indicates the heat of transfer by differential scanning calorimetry (DSC), and the number average molecular weight (Mn) is the value determined by gel permeation chromatography (GPC). This is a value measured in terms of standard polyethylene or polystyrene, and more specifically, a value measured under the following conditions.

Column used JORD I -SAEULE 500 x 10 L I NEAR Mobile phase 1,2-dichlorobenzene benzene (135 ° C), Flow rate 5 ml / min Detector Differential refractometer

Hereinafter, _t detailing as below Orefin polymer having a cyclic structure The olefin polymer having a cyclic structure is preferably a lower alkene having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms ( _α -olefin, in a broad sense, acyclic olefin), and a carbon atom of 3 to 17, preferably Is a copolymer with a cyclic and / or polycyclic compound having at least one double bond of 5 to 12 (cyclic (cyclo) olefin), which is colorless and transparent and has a high light transmittance. . Examples of the lower alkene constituting the polymer include ethylene, propylene and butylene, and examples of the cyclic olefin include norbo <^ renene, tetracyclododecene, dicyclopentadiene, and cyclohexene. This olefin polymer having a cyclic structure can be used, for example, as a catalyst for a meta-opening catalyst, a Ziegler-based catalyst, and a catalyst for metathesis polymerization, that is, double bond opening and ring-opening polymerization. It is a polymer obtained by the polymerization method used. Examples of the synthesis of the olefin polymer having this structure are described in JP-A-5-33932, JP-A-5-92223, JP-A-6-27171628 Japanese Patent Application Publication No. 20-3799, Japanese Patent Application No. 407,790, Japanese Patent Application No. 2831,644, Japanese Patent Application Publication No. It is disclosed in the specification of Japanese Patent No. 1564644 and Japanese Patent Application Laid-Open No. 7-25315.

According to these documents, one or more monomers of the above-mentioned cyclic olefins may be combined with one of the above-mentioned acyclic olefins at a temperature of 180-150 ° C, preferably 20-80 ° C. It is obtained by polymerizing at C at a pressure of 0.01 to 64 bar in the presence of a co-catalyst such as aluminoxane, for example, a catalyst consisting of at least one meta-metacene of zirconium or hafnium. Other useful polymers are described in U.S. Pat. No. 3,172,622, and include hydrogenated polymers and copolymers of styrene and dicyclopentene. Can be used.

In the state where the metallocene catalyst is dissolved in an inert hydrocarbon such as an aliphatic or aromatic hydrocarbon, the metallocene catalyst is activated.For example, the metametallic catalyst is dissolved in toluene and the pre-activation and reaction are performed in a solvent. Is performed. The important properties of the olefin polymer having a cyclic structure are its softening point, melting point, viscosity, dielectric properties, and non-offset temperature range. Transparency. These can be advantageously adjusted by the type of monomer or comonomer—comonomer ratio, molecular weight, molecular weight distribution, hybrid polymer, blend and additives.

The reaction molar ratio of the acyclic olefin to the cyclic olefin can be varied over a wide range depending on the intended olefin polymer having a cyclic structure, and is preferably 50: 1 to 1:50. It is particularly preferably adjusted to 20: 1 to 1:20.

For example, when a copolymer component is charged with two kinds of compounds, ie, ethylene as an acyclic olefin and norbornene as a cyclic olefin, the reaction is carried out. The glass transition temperature of the olefin polymer having a cyclic structure of the reaction product ( Tg) is greatly affected by the proportions of these ingredients, and increasing the content of norportene tends to increase Tg. For example, norbornene can be obtained 15 mol% or less (ethylene 85 mole ^_0/0 than on) if the composition of the Tg gar 20 ° C over 65 ° C below the copolymer, whereas, 15 mol of norbornene %, It is possible to obtain a copolymer having a Tg of more than 65 ° C and not more than 180 ° C. Properties such as number average molecular weight are adjusted as known from the literature.

The olefin polymer having a cyclic structure used in the present invention is constituted as follows. That is, as the binder resin of the core material, an olefin polymer having an unmodified cyclic structure and an olefin polymer having an acid-modified cyclic structure are used in a weight ratio of 95: 5 to 5:95. Preferably, it is configured. Such an olefin polymer having an invariant cyclic structure has a number average molecular weight (Mn; measured by GPC by polyethylene conversion; the same applies hereinafter) of 100 to 20,000, preferably 1,000 to 10,000. 000 or less, a weight average molecular weight (Mw) of 200 or more and 40,000 or less, preferably 6,000 or more and 30,000 or less, and a glass transition temperature (T g) of -20 ° C to 65 ° C, Preferably it is 40 ° C or more and 65 ° C or less.

On the other hand, the olefin polymer having an acid-modified cyclic structure based on the olefin polymer having an unmodified cyclic structure as a base resin has a number average molecular weight (Mn) of 100 or more and 20,000 or less, preferably 1, 000 or more and 10,000 or less And a weight average molecular weight (Mw) of 300 to 80,000, preferably 3,000 to 40,000, and a glass transition temperature (Tg) of -20 ° C to 65 ° C, preferably Is 40 or more and 65 ° C or less, and the acid value is 5-50. In order to secure the fixing property and obtain a wide non-offset temperature range which can be sufficiently used for practical use, the composition of the above-mentioned olefin polymer having a cyclic structure is preferably as follows.

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 polymer having a cyclic structure may be a mixture of the polymer (a) and the polymer (b), or may have a single peak molecular weight distribution and a number average of less than 7,500. A force having a polymer fraction having a molecular weight and a polymer fraction having a number average molecular weight of 7,500 or more, or a molecular weight distribution having two or more peaks, and a polymer fraction having at least one peak among 7,7 The polymer fraction having a number average molecular weight of less than 500 and having other peaks may have a number average molecular weight of 7,500 or more.

Thus, the olefin polymer having a cyclic structure is composed of a low-viscosity (low-molecular-weight) polymer or polymer fraction (a) and a high-viscosity (high-molecular-weight) polymer or polymer fraction (b). The reason for this is that the non-offset temperature range extends to both high and low temperatures, resulting in improved toner fixability during high-speed copying and improved fixability at low and low pressures simultaneously.

The polymer or polymer fraction (a) (hereinafter referred to as “component a”) has a number average molecular weight {measured in terms of polyethylene by GPC (gel permeation chromatography), and the same applies hereinafter] of less than 7,500, preferably 1, 000 to less than 7,500, more preferably 2,000 to less than 7,500; weight average molecular weight is less than 15,000, preferably less than 1,000 to less than 15,000, more preferably less than 4,000 to 15,000. Full; intrinsic viscosity (i.v .; intrinsic viscosity at 135 ° C when 1.0 g of the polymer is uniformly dissolved in 10 OmL of decalin) is less than 0.25 dl / g; glass transition point (T g) is preferably below 70 ° C.

On the other hand, the polymer or polymer fraction (b) (hereinafter referred to as component b) has a number average molecular weight of 7,500 or more, preferably 7,500 to 50,000; a weight average molecular weight of 15,000 or more, Preferably 15,000 to 500,000; intrinsic viscosity (iv) is 0.25 dl / g or more.

Further, the content of the component b is less than 50% by weight, preferably 5 to 35% by weight of the whole binder resin. Component b imparts structural viscosity to the toner and thereby has the effect of preventing offset and improving the adhesiveness to the substrate to be copied such as paper 'film. /. In the above case, the uniform kneading property is extremely reduced, and the toner performance is hindered. In other words, it becomes difficult to obtain a high quality, that is, a clear image with high fixing strength and excellent heat response, or the mechanical pulverizability decreases, and it becomes technically difficult to obtain a particle size required for the toner.

Here, the polymer or polymer fraction refers to each polymer component before mixing when the olefin polymer having a cyclic structure is composed of a mixture of different components such as various number average molecular weights. In other cases, this refers to a polymer category in which the final synthesis product is separated by an appropriate means such as GPC. When these polymer fractions are monodisperse or nearly monodisperse, a number average molecular weight (Mn) of 7,500 is almost equivalent to a weight average molecular weight (Mw) of 15,000.

To extend the non-offset temperature range to the lower temperature side, the low-viscosity component a constituting the olefin polymer having a cyclic structure contributes, and conversely, to increase the non-offset temperature range to the higher temperature side, the high-viscosity component b contributes. In order to more effectively extend the non-offset temperature range to the higher temperature side, the presence of a high-viscosity component b having a number average molecular weight of 20,000 or more is preferred.

When the total amount of the binder resin is 100 parts by weight, the content of each of the components a and b constituting the olefin polymer is at least 0.5 part by weight, particularly preferably 5 to 100 parts by weight. If both are less than 0.5 parts by weight, it tends to be difficult to obtain a practically wide non-offset temperature range.

The high-viscosity (high-molecular-weight) and low-viscosity (low-molecular-weight) olefin polymers having a cyclic structure have the number average molecular weight (Mn), weight average molecular weight (Mw), MwZMn showing the degree of dispersion of molecular weight distribution due to its viscosity (iv) has a small value of 1 to 2.5. That is, the toner has a high heat response due to monodispersion and close to monodispersion, and therefore has a strong fixing strength. In addition to being able to fix the toner at low temperature and low pressure, the toner has good storage stability, vented toner properties, uniform charge distribution, and stable electric charge, which indicates constant charge and charge removal efficiency. Has contributed. Here, particularly when the polymer or polymer fraction having a low viscosity is monodisperse or close to monodisperse, heat response properties as a so-called toner such as instantaneous melting and coagulation behavior are excellent, which is preferable.

In addition, since the olefin polymer having a cyclic structure is colorless and transparent and has high light transmittance, even if the three primary color pigments of yellow, cyan, and magenta are added, sufficient transparency is maintained, and the color toner is used as a color toner. Already applied. In addition, the olefin polymer has a very small heat of fusion as measured by the DSC method (differential scanning calorimetry), so that energy consumption for fixing the toner can be expected to be greatly reduced.

Further, by introducing a carboxyl group into the olefin polymer having a cyclic structure, that is, performing acid modification with a carboxylic acid or a carboxylic anhydride, the compatibility with other resins is improved, Can improve the dispersibility of the pigment. By the introduction of such a carboxyl group, the adhesiveness of the toner to the substrate to be copied such as paper or film can be improved and the fixing property can be increased.

As a method for introducing a carboxyl group, a two-step reaction method in which an olefin polymer having a cyclic structure is first prepared and then a carboxyl group is introduced is advantageous. There are at least two ways to introduce this hapoxyl group. One is to oxidize an alkyl group such as a methyl group at the terminal of the polymer by a melt air oxidation method to form a carboxyl group. However, in this method, it is difficult to introduce a large number of carboxyl groups in the case of an olefin polymer having a cyclic structure synthesized by a meta-mouth catalyst, since there is almost no branching.

Specifically, by weight relative to the Orefin polymer having a cyclic structure, the graph DOO rate is preferably 1 to 5 wt ^_0/0, as particularly preferably a 3-5% by weight, the force carboxylic acid Or carboxylic anhydride, preferably maleic anhydride, acrylic acid or Methacrylic acid is graft-polymerized using a peroxide such as t-butanol peroxide as an initiator to introduce a carboxyl group. If the amount is less than 1% by weight, the above-mentioned effects such as the improvement in compatibility are not sufficient. On the other hand, if the amount exceeds 5% by weight, intermolecular crosslinking occurs in the olefin polymer to increase the molecular weight, and the kneadability and grindability become impractical. In addition, it also exhibits extreme yellow discoloration and devitrification, and thus tends to be unsuitable for color toners requiring colorless transparency. A similar improvement can be realized by introducing a hydroxyl group and an amino group by a known method.

Further, a cross-linked structure can be introduced into the olefin polymer having a cyclic structure in order to improve the fixing property of the toner. One of the methods for introducing this crosslinked structure is to use acyclic olefins and cyclic olefins together with cyclopentadiene, cyclohexadiene, norbornadiene, tetracyclide dodegen, butadiene and the like during the polymerization of the olefin polymer. By terpolymerization by adding a monomer. According to this method, the olefin polymer has an active terminal without a crosslinking agent, and is functionalized by having a crosslinked structure by a known chemical reaction such as oxidation or epoxidation or by adding a crosslinking agent. You.

Another crosslinking method is to add a metal such as zinc, copper, or calcium to the above-described carboxyl group-introduced cyclic polymer having a cyclic structure, and then mix and melt the mixed polymer with a twin-screw extruder to form the metal into fine particles. To give a crosslinked structure by dispersing in a polymer to form an ionomer. The ionomer technology itself discloses a terpolymer of carboxyl-containing ethylene that can be partially or completely neutralized to form a divalent metal salt, for example, to obtain toughness. Japanese Patent Application Laid-Open No. 6-500348 discloses a polyester resin molded article containing an ionomer of an unsaturated carboxylic acid for the same purpose. Approximately 20 to 80% is reported to be neutralized with zinc, cobalt, nickel, aluminum or copper (II).

As for the core material, a carboxyl group-introduced, that is, an acid-modified olefin polymer having a cyclic structure is added to the olefin polymer having a cyclic structure, and the olefin polymer is added with 5 to 95% by weight. Is also good. This addition is effective in fixing, non-offset temperature It is an effective means for securing

(2) Colorant

As a coloring agent, carbon black, diazo yellow, phthalocyanine blue, quinatalidone, riichimin 6B, monoazo red, perylene, etc. used in conventional toners for monochrome or color copying machines can be combined with the core material. it can.

(3) Function-imparting agent

Various polar or non-polar waxes can be blended as a function-imparting agent in order to expand the non-offset temperature range and enhance the non-offset property of the toner. Examples of polar waxes include amide wax, carnauba wax, higher fatty acids and their esters, higher fatty acid metal stones, partially saponified higher fatty acid esters, and higher aliphatic alcohols. On the other hand, non-polar waxes such as polyolefin wax and paraffin wax And at least one wax selected from these can be used as the function-imparting agent.

Among various waxes, a mixture of a fatty acid amide wax, an oxidized polyethylene wax, an acid-modified polypropylene wax, and an oxidized / non-oxidized polyethylene wax is preferable from the viewpoint of obtaining a wide non-offset temperature range.

In order to improve the toner performance by expanding the non-offset temperature range of the toner, it is preferable to use a wax as described below. That is, it is preferable to use two or more kinds of waxes having melting points (peak temperatures in differential scanning calorimetry (DSC)) in the range of 80 to 140 ° C and different melting points. If the melting point is lower than 80 ° C., a problem of blocking due to a low melting point tends to occur when the toner is used. On the other hand, since the function-imparting agent is required to be completely melted at a kneading temperature exceeding the softening point of the binder resin, the softening point of the olefin polymer having a cyclic structure which is a main component of the binder resin (approximately 135 ° C. to 140 ° C.), and the upper limit of the melting point is preferably 140 ° C. Specifically, two or more fatty acid amide-based or hydrocarbon-based waxes exemplified below are selected and used. ①Wax with polar group

Various fatty acid amide waxes, for example, araquinic acid monoamide (melting point 110 ° C), beuyuic acid monoamide (melting point 115 ° C), N, N'-dioleylsepasamide

(Melting point 115 ° C), Ν, Ν'-dioleyl adipic amide (melting point 119 ° C), N, Ν'-distearyl isophthalic amide (melting point 1229 ° C); Oxidized polypropylene, such as polyethylene oxide wax (melting point 1 16 ° C); acid-modified polyolefin resin, such as acid-modified polypropylene wax (melting point 1 38 ° C); carnaubax (melting point about 80 ° C), oxidation There are mixtures of non-oxidized polyethylene waxes.

② Non-polar '14 (no polar group) wax

Olefin wax, which is a hydrocarbon wax, 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: about 98 ° C), There is mycrocrystalline wax (melting point 80-100 ° C). As a function-imparting agent for preventing the offset phenomenon, a silicone oil having a releasing effect may be used in combination with the above pettus, as long as the effect of the present invention is not impaired.

(4) Charge control agent

Nig mouth dye, fatty acid modified nig mouth dye, metal-containing nig mouth dye, metal-containing fatty acid modified nig mouth dye, 3,5-di-tert-butylsalicylic acid complex, quaternary ammonium salt, triphenyl Conventionally known charge control agents such as methane dyes and azochrome complexes can be incorporated into the core material. In addition, as described later, when the charge adjusting agent is mixed with the outer shell material, the charge adjusting agent can be omitted from the core material.

(5) Other additives

If necessary, in addition to the above toner components, colloidal silica (fumed silica) Fluids such as aluminum oxide and titanium oxide, and lubricants composed of fatty acid metal salts such as barium stearate, calcium stearate, and barium laurate, as long as the effects of this effort are not impaired. It can be blended into materials.

(6) Amount of each component

The compounding amounts of the above components in the core material are the same as the general prescriptions for toners for electrostatic image developing type copiers and printers, and are as shown in Table 1 below.

—Table 1 —General composition of various toners

(Unit: Weight Fat Colorant Charge control agent Concealing agent Magnetic powder Solvent Dry 2-component system 50-100 0 ~ 20 0 ~: 10 0 ~ 20 Dry non-magnetic

1-component system 50-100 0 ~ 20 0 ~: 100 ~ 20

Formula magnetism

1-component system 0 ~ 100 0 ~ 20 0 ~ 0 0 ~ 20 0 ~ 60

Dry polymerization system 50-100 0-20 0-10 0-20

Liquid toner 15-50 0 ~: 100 ~ 50 ~ 10 50-70 Liquid toner 15-50 0 ~ 100 ~ 50 ~ 50 50 ~ 70

[B] The material constituting the outer shell material of the microcapsule toner particles

The outer shell material contains a binder resin as an essential component, and may further contain a function-imparting agent, a charge adjusting agent, and other additives as optional components.

(1) Binder resin

As a binder resin constituting the outer shell material of the shell portion of the microcapsule toner particles, the following binder resin for fixing, preferably an olefin polymer having a cyclic structure, is used. These are resins having higher storage stability because they have a higher melting point or softening point than the binder constituting the core material described above.

Examples of the binder resin for fixing include styrene or a derivative thereof such as substituted styrene, (meth) acrylic acid, (meth) acrylic acid ester, maleic anhydride or maleic anhydride. Ter and other derivatives, nitrogen-containing bur compounds such as maleic anhydride amide, butyl pyridine and N-vinylimidazole; Homopolymer or copolymer of olefin monomer such as dilidene monomer, ethylene, propylene, polyester, epoxy resin, polycarbonate, polyamide, polyurethane, polyurea, rosin, modified rosin, phenol resin, melamine resin, polyphenylene oxide, Examples thereof include condensation polymers such as polyphenylene oxide, terpene resins, aliphatic or alicyclic hydrocarbon resins, and petroleum resins. These can be used alone or in combination of two or more.

In order to prevent the offset phenomenon of transfer to the heat roll and to further improve the storage stability, the following olefin polymer having a cyclic structure is used as the binder resin for the outer shell material. Preferably.

That is, as the binder resin of the outer shell material, an olefin polymer having an unmodified cyclic structure is preferable, but if the glass transition temperature is 60 ° C or higher, the storage stability of the toner is sufficiently ensured. The entire amount of the binder resin may be replaced by an olefin polymer having a cyclic structure in which a carboxyl group has been introduced, that is, a carboxylic acid modification. The olefin polymer having an unmodified cyclic structure has a number average molecular weight (Mn) of 1,000 to 100,000, preferably 2,000 to 50,000, and a weight average molecular weight (Mw). 2,000 to 200,000, preferably 4,000 to 100,000, and a glass transition temperature (T g) of 60 to 180 ° C, preferably 60 to 80 ° C It is as follows. On the other hand, the olefin polymer having a carboxylic acid-modified cyclic structure has a number average molecular weight (Mn) of 1,000 to 100,000, preferably 2,000 to 50,000, and a weight average molecular weight (Mn) of 2,000 to 50,000. It has a molecular weight (Mw) of 3,000 or more and 300,000 or less, preferably 6,000 or more and 200,000 or less, an acid value of 5 to 50 (rngKOH / g), and a glass transition temperature (T _g ) of 60 °. It is not less than C and not more than 180 ° C, preferably not less than 60 ° C and not more than 80 ° C. If the glass transition temperature is lower than 60 ° C, the storage stability of the toner particles becomes more problematic, while if it exceeds 180 ° C, the melting point increases. The fixability tends to be poor. On the other hand, 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 becomes difficult to secure necessary solubility in a solvent. On the other hand, if the acid value is less than 5, the effects of improving the compatibility of the resin and improving the adhesion to paper are not sufficient. If the acid value is more than 50, the discoloration becomes strong and the hygroscopicity becomes high, so that it is not practical.

For the above-mentioned olefin polymer having a cyclic structure, various properties other than the glass transition temperature and the number average molecular weight, modified products, crosslinked products, etc. are described in the description of the olefin polymer having a cyclic structure used for the core material described above. The carboxylic acid-modified olefin polymer having a cyclic structure also has a carboxyl group introduction method, the type of carboxylic acid or carboxylic anhydride used for the modification, the graft ratio, and the like described above. Since the core material is the same as that described above, the description is omitted here.

(2) Function-imparting agent

In order to further improve the non-offset property of the toner particle surface by expanding the non-offset temperature range, the outer shell material is made of the same functionalizing agent (wax, silicone oil) used for the core material described above. Can be blended. The preferred modes of use described above also apply to the function-imparting agents blended in the shell material.

(3) Charge control agent

The same charge control agent as used in the core material described above can be blended in the outer shell material. Usually, if it is added to the outer shell material, it is omitted from the core material.

(4) External additives

If necessary, the surface of the outer shell material of the microcapsule toner particles can be coated with an external additive. External additives include fine particles of silica such as colloidal silica (including fumed silica), fluidizing agents such as anolemminium oxide and titanium oxide, and lubricants composed of fatty acid metal salts such as palladium stearate, calcium stearate, and barium laurate. so Yes, these can be used alone or in combination of two or more. Further, it is preferable to use those which have been subjected to hydrophobic treatment.

The amount of the external additive is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the toner particles.

When the outer shell material is coated with an external additive, a solution containing the external additive is applied to the surface of the particles, or attached to the surface by other methods.

(5) Amount of each component

The blending amounts of the above components in the outer shell material are as shown in Table 1 except for the coloring agent.

[C] Microcapsule toner particles

The microcapsule toner particles have a capsule-type so-called core-shell structure in which a core material is covered with an outer shell material. Average particle size (diameter) is preferably _3~10 μ ηι of the whole grain, shell thickness. ((Power capsule OD - Kakuzai径) X 1/2) is from 0.1 to 0 5 111 are preferred.

In the present invention, as a combination of a core material and an outer shell material for the binder resin,

(a) nuclear material: Orefin polymer having a cyclic structure ^{^{(_ 2 0C≤Tg ^ 6 5 °}} C,

100≤Mn≤20,000),

Outer shell material: binder resin for fixing;

(b) nuclear material: Orefin polymer having a cyclic structure (one ^{_{^{2 0 ° C≤T g ^ 6 5}}} ° C,

100≤Mn≤20,000) and a mixture of heat fixing resin and / or pressure fixing resin,

Outer shell material: olefin polymer with cyclic structure (60 ° C T g≤180 ° Cs

l, 000≤Mn≤100,000);

(c) Core material: olefin polymer having a cyclic structure ( ²⁰ ° C≤T g≤65 ° C,

100≤Mn≤20,000), Two

20 Outer shell material: olefin polymer with cyclic structure (60 ° C≤T _g ≤180 ° C _S

1, 000≤Mn≤100, 000);

There are three embodiments.

As a result of compounding in combination with the various types of crystalline / amorphous resins exemplified as the olefin polymer having a cyclic structure or the fixing resin of the above [A] (1) having relatively good compatibility therewith, The properties such as transparency, low-temperature fixability, and mechanical shock resistance, which are important as the toner performance of the olefin polymer, can be obtained. As the outer shell material, an acid-modified olefin polymer having a cyclic structure, or another fixing resin described in [B] (1), or a mixture thereof can be used.

In the case of the above-mentioned embodiment (c) in which an olefin polymer having a cyclic structure is used for both the outer shell material and the core material, the above characteristics are fully exhibited as toner performance. Here, the most preferred embodiments of the toner particles are as follows. Binder resin for core material: ethylene 'norbornene copolymer or carboxylic acid-modified ethylene / norbornene copolymer (acid value about 10 mgKOH / g), glass transition temperature (Tg) 40-59 ° C, number Average molecular weight (Mn) is 1,000 or more: LO, 000, weight average molecular weight (Mw) is 6,000 to 30,000, polydispersity (weight average molecular weight (Mw) Z number average molecular weight (Mn))

less than 10,

A polymerization molar ratio of 85/15 to 95/5 Binder resin for outer shell material: carboxylic acid-modified ethylene-norpoleneene copolymer Glass transition temperature (Tg) is 60-80 ° C, number average molecular weight (Mn) is 2,000-50,000, weight average molecular weight (Mw ) Is 6,000 to 200,000 polydispersity (Mw / Mn) is 4 to 10,

The polymerization molar ratio is

75 / 25-85Z15, acid value about 1 OmgKOH / g, soluble in methyl ethyl ketone (MEK).

[D] Method for producing microcapsule toner particles

The production method of the present invention is a further improvement of the reprecipitation method proposed in the specification of Japanese Patent Application No. 10-312215 to obtain toner particles having a uniform (sharp) particle size distribution. be able to.

That is, the production method according to the present invention is directed to a method for producing an electrostatic image comprising microscopic pushel toner particles composed of a core material composed of a colorant and a binder resin and an outer shell material composed of the binder resin and covering the core material. In the production of a developing toner, a core material solution in which a colorant is dispersed in a good solvent solution of a binder resin forming a core material is converted into mist-like fine droplets to form a binder forming an outer shell material. It is characterized in that it is injected and dropped into a poor solvent solution of the resin to be encapsulated for encapsulation.

(1) Nozzle for spraying The method of spraying and dropping the fine particle droplets of the core material solution into the outer shell material solution uses a spray nozzle and a nozzle for an ink jet printer. The method can be exemplified as suitable. With such a nozzle, it can be turned into a nearly spherical fine droplet having an estimated diameter of 2 to 50 microns.

(1) Spray nozzle Spray nozzles are commercially available for spraying insecticides and fungicides, and have a pore size of 2 to 50 m, or 0.2 to 0 in the case of the impingement fine atomizing nozzle described later. It is preferable to select one with 5 瞧 φ.

Among various spray nozzles, two injection holes with a hole diameter of about 0.45 ram are nozzles installed at positions where the injection direction is about 120 degrees to each other, and the jets collide and collide The impingement type fine fog nozzle of the embodiment is particularly preferred. An injection nozzle of such an embodiment is described, for example, in Japanese Patent Publication No. Hei 4-9-1104.

FIG. 1 is an external view of a collision type fine mist nozzle, and FIG. 2 is a partial cross-sectional view showing a form of an injection hole at a tip of the collision type fine mist nozzle.

In FIG. 1, two injection holes (11) are attached to the nozzle (1) at a position where the intersection angle of the extension of the droplet passage becomes 120 °.

In FIG. 2, each injection hole (11) has an inner / outer double tube structure, in which droplets are ejected from the inner tube (11a) and compressed air is ejected from the outer tube (lib). The droplets ejected from the inner tube (11a) collide with the air ejected from the outer tube (lib) and are atomized, and the droplets atomized in the next step are ejected from the other ejection hole and similarly. By colliding with the atomized droplets, they are further atomized and homogenized, and can be formed into droplets having an estimated diameter of 2 to 50 μm. The air pressure applied around the spray nozzle is preferably from 0.3 to 0.5 MPa. The supply of the nuclear material solution to the nozzle is performed by sucking up from the suction tank.

(2) Ink jet printer nozzle The ink jet printer nozzle used in the present invention electrostatically accelerates fine particles of ink ejected from the nozzle and deflects them to form a dot matrix character on paper. This is the same as the mechanism of the ink ejection nozzles used in printers, commonly known as inkjet printers. That is, a means for generating a high pressure instantaneously in a nozzle for generating a droplet of nuclear material is provided, The nuclear material droplet is caused to fly toward the outer shell solution.

Regarding such a nozzle, specifically, the method of ejecting the droplet is a piezoelectric element (piezo) type volume change, an electric field control by a multi-level electrostatic charge method, or a thermal element type volume change (so-called “Vaplet Jet (registered trademark)”). )), And a nozzle of a piezoelectric element (piezo) type volume change type is particularly preferable. Further, the form of the nozzle is preferably one in which the number of holes is several to 50 and each hole diameter is 10 to 30 μηι. Note that the size of the ejected droplet is a fine particle with an estimated diameter of 5 to 50 μm even if the nozzle hole diameter is large.

(3) Solvent (1) Solvent for core material A good solvent for the binder resin constituting the core material, that is, the binder resin contained in the core material, for example, an olefin polymer having an unmodified cyclic structure (eg, ethylene-norbornene copolymer) And benzene, toluene, and xylene. In the case of using an ink jet type nozzle, an aromatic solvent is not preferable from the viewpoint of nozzle member protection, and a naphthenic solvent which is a mixture of an aliphatic hydrocarbon and an alicyclic hydrocarbon is preferable. Is preferred. Such naphthenic solvents, alkanes C ₆ -C _9, a cycloalkane component, for example commercially available from Ekuson Chemical Co. under the trade name "Etasoru" Ekuso Lumpur DSP 100/140, D30, D40, D80 , D110 Grades, etc., and each component and composition are different. The boiling point is 120 to 180 ° C at 50% of normal pressure. When a carboxylic acid-modified cyclic polymer having a cyclic structure is used, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) are used. Further, the concentration of the binder resin in the solution is preferably 5 to 30% by weight in order to adjust the solution viscosity to an appropriate level to obtain spherical particles having an optimum particle size.

②Shell material solvent 03010942

24 Examples of poor solvents for the binder resin that constitutes the outer shell material, that is, solvents that have the ability to dissolve the binder resin contained in the outer shell material but have limited solubility, include MEK :, MI BK :, and Xesol. Examples can be given. In the case of using an unmodified olefin polymer having a cyclic structure, a naphthene solvent such as etasol or the like, which hardly dissolves the olefin polymer having a carboxylic acid-modified cyclic structure as a core material component, is used. The concentration of the binder resin in the solution is preferably set to 1 to 5% by weight in order to adhere an appropriate amount to the periphery of the core material.

(3) Specific Production Example A method for producing toner particles using a spray nozzle (solvent reprecipitation method) according to the present invention is specifically described as follows.

20 to 35% by weight of a olefin polymer having a cyclic structure constituting a core material and 2 to 3.5% by weight of a function-imparting agent are added to a solvent such as toluene at 61.5 to 78% by weight at 25 to 30 ° C. After adding and dissolving at a temperature of above, prepare a solution (Solution A) in which 1-2% by weight of colorant is dispersed by a bead mill or the like. On the other hand, 1.8 to 2.2% by weight of a olefin polymer having a cyclic structure constituting the outer shell material and 0.015 to 0.025% by weight of a charge control agent such as methyl ethyl ketone (MEK) are used. Prepare a solution (Solution B) dissolved in about 98% by weight of the solvent.

Next, liquid A is mixed with air from two spray nozzles with a liquid flow path with an outlet hole diameter of 0.45 ram and an air flow path around it as shown in Figs. The precipitate is obtained by spraying under high-speed stirring into a vat containing the liquid. At that time, the scattered mist is pulled by an exhaust pump and collected in the B liquid trap. Next, it is separated from the solvent by a filter, and finally the residual solvent is distilled off by a high-temperature vacuum dryer to granulate. Thus, the shape is almost spherical, the average particle size is 4 to 10 _μm , the particle size distribution is ² to 12 / ίΐη (σ = 3σ when expressed by standard deviation), and the thickness of the outer shell material 0. 2~0. 5 !! 1 _c can be obtained microcapsule toner particles (by weight as measured by solvent component dissociation method) Further, hydrophobic silica is externally added for use in a developer.

The method for producing toner particles using a nozzle for an ink jet printer also conforms to the above.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an external view of a collision type fine fog nozzle.

FIG. 2 is a partial cross-sectional view showing the form of an injection hole at the tip of a collision type fine mist nozzle. The reference numerals shown in FIGS. 1 and 2 are as follows.

1 Collision type fog nozzle

1 1 Injection hole at the tip of collision type fine fog nozzle

1 1 a Inner pipe of injection hole

1 1 b Outer pipe of injection hole

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Dry one-component and two-component dry toners were prepared as described below. Examples 1 and 3 are examples of manufacturing a microphone-capsule toner using a spray nozzle, and Examples 2 and 4 are examples of manufacturing a micro-forced toner using a nozzle for an ink jet printer. It is an example.

[Example 1] (using spray nozzle)

①Preparation of resin active substance A

Glass transition temperature as Orefin polymer having a cyclic structure (T _g) of about 6 5 ° C, a weight average molecular weight (Mw) of from about 9 0 0 0 a is Ticona Corp. "Topas TMJ (trade name) 9 3 wt ^_0/0, functional base to Nin acid amide wax as imparting agent (Nippon fine Chemical Co., Ltd. "BNT 2 2 H") 2 wt ^_0/0, the mixture powder (Clariant oxide ■ unoxidized polyethylene wax "Seridasuto 3 7 1 5 F ”(brand name)) 2 weight. / ₀ and blue 3% by weight of a coloring agent (“Toner Cyan BGj” manufactured by Clariant) was kneaded with a twin-screw extruder to obtain a resin precursor A.

② Preparation of solution A (nuclear material) ''

To 75 parts by weight of toluene, 25 parts by weight of the resin precursor A was gradually added and dissolved at a temperature of 30 ° C. and a stirring speed of 20 O rpm. Thereafter, the resin component in the solution was dispersed with an ultrasonic cleaner, and then the mixture was stirred with a mixer at a stirring speed of 950 Orpm to obtain a solution. Then, this solution was subjected to pressure filtration with 20 Omesh to remove foreign substances. The viscosity of the solution A measured by a B-type viscometer was 17.8 cP (centrifuge, ') (rotor No. 1, 60 rpm, 20.C).

③Preparation of resin material B

As a olefin polymer having a cyclic structure, a glass transition temperature (Tg) of 65 ° C and a weight-average molecular weight (Mw) of 50,000 manufactured by Ticona, Inc. The Tg is 65 ° C, the Mw is about 50,000, and the acid value is about 10 mgKOH / g. Ticona “Topas TBG” 98% by weight and a charge control agent (Orient Chemical “E-84” ( (Trade name)) 2% by weight was kneaded in the same twin-screw extruder as above to obtain a resin precursor B.

液 Preparation of liquid B (shell material)

5 parts by weight of the resin base B was dissolved in 95 parts by weight of methyl ethyl ketone to obtain a solution B.

⑤Granulation process

The above solution A was sprayed onto the above solution B at an air pressure of 0.3 to 0.5 MPa using a collision type fine fog nozzle (“AKIJET” manufactured by Ikeuchi Co., Ltd.) and dropped. During this time, the solution B was stirred by a stirrer at a speed of 30 Orpm.

The dropping time was about 3 minutes, and the solution was dropped until no liquid remained in the funnel to obtain a precipitate. After the dropwise addition, stirring was continued for 5 minutes as it was. A Teflon (registered trademark) funnel was attached to the upper surface, and the scattered toner particles were sucked by a vacuum pump attached to the end. On the suction side, it is placed in a trap containing MEK and bubbling to capture fine particles. 2003/010942

27

The solution B dropped was filtered by suction with a filter paper capable of holding up to 3 / x m. During the filtration of the solution B, the solution was replaced while adding a small amount of alcohol, and finally, filtration was performed while washing with only the alcohol.

The residue was removed from the residue by a high-vacuum drier to obtain Microforce Puser toner particles.

The average particle size of the obtained toner particles is about 7 m, and the particle size distribution is in the range of 3.5 to 11 m. All the particles converge, and have uniformity that does not require classification of coarse particles and fine particles. It turned out that the productivity was excellent. In addition, the shape of the toner particles was confirmed to be substantially spherical by observation with a scanning electron microscope.

The average particle size of the toner particles is a numerical value obtained by a laser diffraction / scattering type particle size distribution analyzer (“LA-700 J” manufactured by Horiba, Ltd.). Particles with a particle size of 3 to 9 m exceeded 90% by volume, and particles with a particle size of 2.3 to 9 zm occupied about 95%. Then, 10 g of toner particles were weighed and collected in 1 liter of methyl ethyl ketone, heated to 50 ° C and stirred for 20 minutes to dissolve the outer shell material, and then hot filtered to remove the solvent. Distill off and measure the remaining weight.

[Example 2] (using ink jet printer nozzles)

(1) The preparation of resin raw material A is the same as in Example 1 above.

② Preparation of solution A (nuclear material)

The solvent is taken into account viscosity, surface tension, Etasoru D_ ³ 0 naphthenic solvents, walk were used D-40. Using these solvents, a solution A (nuclear material) solution was prepared so as to have a polymer concentration of 15 to 20%. After the preparation, the resin component in the solution was dispersed by an ultrasonic washing machine, and thereafter, the mixture was stirred by a mixer at a speed of 950 rpm.

Thereafter, pressure filtration is performed using a filter paper having a hole diameter of 10 / zm to remove foreign substances. Thereafter, defoaming was performed to remove dissolved air.

There are about 20 nozzles for inkjet printers with a pore size of 15 μιη Was used.

(3) Preparation of resin base B is the same as in Example 1 above.

液 Preparation of solution B (outer shell material) is the same as in Example 1 above.

⑤Granulation process

After filling the liquid A into the ink jet printer nozzle (piezoelectric (piezo) type volume change method), it was sprayed for about 20 minutes into the liquid B stirred at a speed of 30 Orpi with a stirrer.

After the injection, the liquid B containing the particles was subjected to suction filtration using a filter paper capable of holding up to 3 im. During the filtration, the solution B in the Buchner funnel was filtered while slowly stirring with a stirring blade. During the filtration, the solution was replaced while adding a small amount of alcohol, and finally, filtration was performed while washing with only alcohol.

The residue was removed from the residue by a high vacuum dryer to obtain a microcapsule toner. When the particle size was confirmed by an electron microscope, the average particle size of the obtained toner particles was about 7 to 8 μιη, and the particle size distribution was 3 to 15 μιη.

[Example 3] (use of horn for spraying)

①Preparation of resin active substance A

As a olefin polymer having a cyclic structure, a glass transition temperature (Tg) of 65 ° C and a weight average molecular weight (Mw) of 50,000 manufactured by Ticona, Inc. a finished products T g is 65 ° C, Mw of about 50, 000, acid value Ticona Corp. of about 10 mgKOH / g "Topas TBG" 93 weight ^_0/0, Yun acid amide wax to the base as a function imparting agent ( Nippon Seika Co., Ltd. "BNT2 2HJ" 2 weight ⁰ % Oxidized and non-oxidized polyethylene wax mixture fine powder not yet (Clariant "Celidust 371 5F" (trade name)) 2% by weight and blue colorant (Clariantone Earthen “Toner Cy an BG”) 3 weights ⁰ / o were kneaded with a -screw extruder to obtain a resin precursor A.

② Preparation of solution A (nuclear material) To 80 parts by weight of methyl ethyl ketone, at a temperature of 30 ° C., at a stirring speed of 200 rpm, 20 parts by weight of the resin base A was gradually added and dissolved. Thereafter, the resin component in the solution was dispersed by an ultrasonic washing machine, and thereafter, the solution was stirred by a mixer at a stirring speed of 9500 rpm to obtain a solution. Next, this solution was subjected to pressure filtration with a 20 O mesh to remove foreign substances. The viscosity of the solution A by a B-type viscometer was 35.5 cP (centipoise) (rotor No. 1, 60 rpm, 20 ° C.).

③Preparation of resin material B

"Topas TB" (trade name) manufactured by Ticona Co., having a glass transition temperature (T g) of about 65 ° C and a weight average molecular weight (Mw) of about 50,000 as an olefin polymer having a cyclic structure. %When,

2% by weight of a charge control agent (“E-84” (trade name) manufactured by Orient Kasei Co., Ltd.) was kneaded with a twin-screw extruder to obtain a resin precursor B.

液 Preparation of liquid B (shell material)

5 wt ^_0/0 of the resin conformal B, was dissolved in Etasoru D-3 0 9 5 parts by weight to obtain a B solution.

Performed in the same manner as in Example 1.

The average particle size of the obtained toner particles is about 8.5 μιη, and the particle size distribution is uniform, with all particles converging in the range of 4.5 to 15 without the need to classify coarse or fine particles. As a result, it was found that the productivity was excellent. The shape of the toner particles was confirmed to be almost spherical by observation with a scanning electron microscope.

The average particle diameter of the toner particles and the thickness of the outer shell material were also measured, measured, or calculated in the same manner as in Example 1. [Example 4] (Using nozzle for inkjet printer)

(1) The preparation of resin raw material A is the same as in Example 3 above.

② Preparation of solution A (nuclear material)

Methyl ethyl ketone was used as the solvent. Solution A (nuclear material) is dissolved using these solvents. A solution was prepared so that the solution had a polymer concentration of 15 to 20%. After the preparation, the resin content in the solution was dispersed by an ultrasonic washing machine, and then the mixture was stirred at a speed of 9500 rpm using a mixer.

Then, it was subjected to pressure filtration using a filter paper having a hole diameter of 10 m to remove foreign substances. Thereafter, defoaming was performed to remove the dissolved air.

The nozzles for ink jet printers used had about 20 holes with a diameter of 15; um.

(3) Preparation of resin base B is the same as in Example 3 above.

液 Preparation of solution B (outer shell material) is the same as in Example 3 above.

⑤Granulation process

The procedure was performed in the same manner as in Example 2. The average particle size of the obtained toner particles was about 7 to 9 μηι, and the particle size distribution was 3 to 20 μηι.

[Comparative Example 1] ("Example 1" of JP-A-2000-147829)

① Preparation of liquid (nuclear material solution)

As a olefin polymer having a cyclic structure, Ticona "Topas T-1936" having a glass transition temperature (Tg) of 49 ° C and a number average molecular weight (Mn) of 2,000, 17% by weight, 1% by weight of Ticona's Topas AG-07, a olefin polymer modified with acrylic acid, having a glass transition temperature (Tg) of 58 ° C and a number average molecular weight (Mn) of 3,700 as an olefin polymer having a cyclic structure If, Nippon Fine Chemical Co., Ltd. "BNT 22H" as a function imparting agent 0.5 weight ^_0/0, manufactured by Clariant "Seridasuto 371 5" and the (trade name) 0.5 ^_0/0, 80% by weight of toluene Sik The mixture was gradually added to an hexane mixed solvent (weight ratio: 50:50) at a temperature of 30 ° C. at a stirring speed of 20 O rpm to dissolve. Thereafter, the beads to the solution; progressively (stainless powder Ashizawa Co. particle size 500 zm) was added, the black coloring agent (manufactured by Mitsubishi Chemical Corporation "Carbon Black MA_ 7j) to 1 weight ^_0/0 At 50 Orpm The mixture was added and dispersed to obtain a liquid A.

② Preparation of solution B (outer shell material solution)

As a olefin polymer having a cyclic structure, its glass transition temperature (Tg) is 6 7 ° C Number average molecular weight (M n) is 4, 6 0 0 a is Ticona Corp. "Topas AG- 0 9" 2wt ^_0/0 and a charge control agent (manufactured by Clariant, "Copy Charge NX" (trade name) ) 0. 0 2 wt% and dissolved in about 9 8 weight ^_0/0 methyl E chill ketone to give a B solution.

③ Granulation process

The liquid A was dropped into the liquid A from a nozzle having a large number of orifices having a diameter of 30 μιη under high-speed stirring to produce particles. At this time, the particle size of the solution dropped was estimated to be 20 to 40. In the case of manufacturing with a kettle with a capacity of 500 liters, 200 liters of solution B is added with 200 liters of solution A at 200 liters at a rate of 5 liters per minute from 100 orifices. A precipitate was obtained by dropwise addition over a period of minutes. The stirring speed of the solution B was set to 200 O rpra. After the completion of the dropping of the solution A, the stirring was continued for 10 minutes following the bow I. Thereafter, the precipitate was separated from the solvent by a filter, and the residual solvent was distilled off with a high-temperature vacuum drier to obtain a micro force toner particle.

The average particle size of the obtained toner particles was about 10 / im, and the particle size distribution was in the range of 3 to 15 / m. The shape was observed by a scanning electron microscope, and it was confirmed that the shape was almost spherical.

[Comparative Example 2]

A toner manufactured by a commercially available air impact pulverization method (so-called jet pulverization).

The average particle size was 7.0 μm, and the particle size distribution was 1.8 to 17 μm. [Comparative Example 3]

This is a toner manufactured by a commercially available mechanical milling method, specifically, a toner for QMSS printer “Majicolor 2CX” (trade name).

[Evaluation of manufactured toner] Using the micro force pusher obtained in Examples 1 to 4 and the toners of Comparative Examples 1 to 3 in a copying machine “FT-5520” manufactured by Ricoh Co., Ltd., the following performance tests were performed and evaluated. did. The results are as shown in Table 2.

(a) Svent toner resistance

Using the toner samples of the examples and comparative examples, an actual printing test was performed on high-quality paper, and actual printing was performed on the developing sleeve and the photoconductor until the toner component reached the allowable limit adhesion amount, and the number of plain papers was compared.

(b) Transferability

The transfer efficiency from the photoreceptor to the high-quality paper, which is the substrate to be copied, was measured by the amount of toner collected after 10,000 actual copies.

(c) Retention

An image was formed on a high-quality paper using each toner, and an unprinted homogeneous paper was placed thereon, and the print was rubbed with a rubbing tester to forcibly transfer the image to the unprinted paper. The fixing speed during image formation was set at 15 OmmZ seconds, and the fixing temperature was set at 150 ° C. The conditions during the friction test were 20 reciprocations under a load of 2 pounds (about 907 g). Using a Macbeth reflection densitometer after rubbing, measure the initial image density before rubbing (A), the transfer density to unprinted paper (B), and the density of the non-image area of paper (C), and calculate the formula [(B—C) ZAX 100 (%)]. The minimum fixing temperature and the minimum fixing pressure at which the transfer rate was 60% or more were measured and compared.

(d) Image quality

Comparative evaluations were made on the image quality of each toner based on the gradation, fine line resolution, and transparency.

① Gradation:

The evaluation was performed based on the number of grayscale identification steps 0 to 16 using an image sample manufactured by DataQuest.

② Fine line resolution:

The evaluation was made based on a fine line pattern of 0 to 600 dpi using an image sample manufactured by DataQuest.

③ O HP permeability: An image was formed on an OHP film for PPC manufactured by Fuji Xerox Co., Ltd. The amount of light transmission in the image area (A) and the non-image area (B) was measured and displayed as AZBX 100 (%).

[0093]

(e) Storage stability

After storing the toner prepared in each formulation under the conditions of 60 ° C and 50% RH (relative humidity) for 8 hours, the mesh residue after sieving with 100 mesh for a certain period of time is divided by the amount of sample used. displayed. The value increases when the toner particles aggregate during storage. This is mainly due to the low melting point substance of 50 ° C or less contained in the toner composition. When the mesh residual amount is 0.5% or less, the symbol “〇” is applied. When the mesh amount exceeds 0.5%, the symbol “X” is applied. Table 2

INDUSTRIAL APPLICABILITY The present invention has the following advantageous effects, and thus has a possibility of being industrially used.

According to the method of the present invention for producing a microcapsule toner using a spray nozzle or a nozzle for an ink jet printer when injecting a core material solution into a shell agent solution, a microcapsule toner having a uniform particle size distribution can be obtained. The resulting toner has good storage stability, provides clear and high-quality images, Excellent transferability, fixability and non-offset properties. In particular, it is excellent in that it has a sufficient fixing property even with a low-temperature heating method.

In addition, even in the case of the heat roll fixing method, it is easy to greatly reduce the amount of heat, which can contribute to energy saving of copying machines. Further, by adding a function-imparting agent having a releasing effect such as silicone oil or wax to the outer shell material, oil supply to the surface of the heat roll becomes unnecessary.

When using a nozzle for an ink jet printer, a naphthenic solvent, which is a mixture of an aliphatic and alicyclic hydrocarbon, should be used as the solvent of the nucleating material solution because the member of the nozzle is easily eroded by an aromatic solvent. Thus, it can be applied to the copying machine of the pressure heating fixing system.

Claims

The scope of the claims

1. Mic lipstick toner particles composed of a core material made of a binder resin containing a colorant and an olefin copolymer having a cyclic structure, and an outer shell material made of the binder resin and covering the core material. In the production of a toner for developing an electrostatic charge image composed of fine particles of a core material solution in which a colorant is dispersed in a good solvent solution of a binder resin constituting the core material, an outer shell material is formed. A method for producing a toner for developing an electrostatic image, wherein the toner is sprayed and dropped into a poor solvent solution of a binder resin.

2. The method for producing a toner according to claim 1, wherein fine particles of the core material solution are ejected and dropped into the outer shell material solution by using a spray nozzle.

3. The method for producing a toner according to claim 1, wherein fine droplets of the nucleus material solution are jetted and dropped into the outer shell material solution using an ink jet printer nozzle.

4. The method of jetting the fine particle droplets of the nucleus material solution into the outer shell material solution using the ink jet printer nozzle is based on the piezoelectric element type volume change, multi-level electrostatic charge type electric field control and thermal element. 4. The method for producing a toner according to claim 3, wherein the method is any one method selected from volumetric changes.

5. The method for producing a toner according to claim 3, wherein the solvent of the core material solution is a naphthenic solvent of a mixture of an aliphatic hydrocarbon and an alicyclic hydrocarbon.

6. Annular binder resin constituting the core material is in the range weight average molecular weight in one 2 0 ° C over 6 5 ^a C following ranges glass transition temperature of 2 0 0 4 or more 0, 0 0 0 less 2. The method for producing a toner according to claim 1, comprising an olefin copolymer having a structure.

2. The method for producing a toner according to claim 1, wherein the olefin copolymer resin having a cyclic structure constituting the nucleus material is a copolymer modified with sulfonic acid or a carboxylic anhydride. The binder resin constituting the outer shell material has a glass transition temperature of 60 ° C or more and 180 ° C or less and a weight average molecular weight of 2,000 or more 200,000. The method for producing a toner according to claim 1, comprising an olefin copolymer having a cyclic structure as follows. 2. The method for producing a toner according to claim 1, wherein the olefin-based copolymer resin having a cyclic structure constituting the outer shell material is a copolymer modified with carboxylic acid or carboxylic anhydride. 0. The method for producing a toner according to claim 1, wherein a mixture of a binder resin constituting the core material and / or a binder resin constituting the outer shell material is used. 10. The toner according to claim 10, wherein the wax is at least one selected from the group consisting of fatty acid amide wax, polyethylene oxide wax, acid-modified polypropylene wax, and a mixture of oxidized and non-oxidized polyethylene wax. Manufacturing method.

12. An electrostatic charge, characterized in that silica fine powder is externally added or applied to the surface of the microphone force-pressed toner particles produced by the method for producing a toner according to claim 1. Image developing toner.