JPH02300764A - Production of toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain good-quality images even in any environment by securely immobilizing charge controllable particles together with resin particles in the form of powder by mechanical impart. CONSTITUTION:A mixture composed of 100pts.wt. coloring particles A, 0.2 to 10.0pts.wt. charge controllable particles and 1 to 30pts.wt. resin particles C having <=0.2 grain size ratio with respect to the coloring particles A is passed through an impact part having the shortest spacing of 0.5 to 10mm under the conditions of 10 to 90 deg.C. The charge controllable particle B and the resin particles C are simultaneously immobilized onto the surfaces of the coloring particles A by the mechanical impact in the impact part. The charge control agent is securely immobilized to the surface of the coloring particles A by combination use of the resin particles C in such a manner. In addition, the charge controllable particles exist uniformly and stably on the individual toner particles and, therefore, the triboelectric charge quantity between the toner particles is extremely uniformized. The uniform and stable electrostatic charge is executed in this way and the environmental resistance is improved. The high-grade copied images are thus obtd. over a long period of time under any conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrostatic image developing l-ner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,691
Specification, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 4
A number of methods are known, as described in Japanese Patent No. 3-24748, etc., but generally a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then The latent image is developed using toner, and after the toner image is transferred to a transfer material such as paper as necessary, it is fixed by heat, pressure, heat and pressure, solvent vapor, etc. to obtain a copy.

The toner is triboelectrically charged to a positive or negative charge depending on the polarity of the electrostatic latent image being developed. To triboelectrically charge the toner, it is also possible to utilize the triboelectricity of chin fat, which is one of the components of the toner, but this method does not allow a sufficient amount of charge to be obtained. Therefore, images obtained by developing with such toners tend to fog (and become unclear. Therefore,
In order to impart sufficient triboelectric charging properties to toner, it is common practice to add a substance called a charge control agent.

Charge control agents known in the technical field today include nigrosine, azine dyes, quaternary ammonium salts, etc. that control toner to be positively charged. On the other hand, there are metal complex salts of monoazo dyes, metal complexes of salicylic acid such as Go, Cr, Fe, etc., which control the toner to be negatively charged. These are usually added to thermoplastic resins, thermally melted and dispersed, and then finely pulverized to adjust the particle size to an appropriate particle size as necessary before use.

However, since it is extremely difficult to uniformly disperse these charge control agents in a thermoplastic resin, there is a problem in that there is a difference in the amount of triboelectric charge between toner particles obtained by pulverization. . For this reason, various methods have been used to make the dispersion more uniform. For example, basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve their compatibility with thermoplastic resins, but often unreacted fatty acids or salt dispersion products are used in toners. It is exposed on the surface and contaminates the carrier or toner carrier. Otherwise, it causes a decrease in toner fluidity, fog, or a decrease in image density. On the other hand, in order to improve the dispersibility of the charge control agent into the resin, a method has also been adopted in which the charge control agent and the resin powder are mechanically pulverized and mixed in advance, and then the mixture is thermally melted and kneaded. However, there is currently a long-awaited improvement in order to avoid the inherent poor dispersion and to obtain sufficient charge uniformity.

Furthermore, Japanese Patent Application Laid-Open No. 58-106554 proposes a method of coating a monodisperse spherical core with a polymer material containing a colorant. One method is to add a monodisperse spherical core to a solution of cyclohexane, methanol, etc. in which a polymer substance and a colorant are dissolved or dispersed, and then coat the core by removing the solvent. Such methods require fairly low amounts of polymeric material in the solvent to obtain good coatings, require equipment for solvent removal, and are expensive. Furthermore, it is technically difficult to avoid particle agglomeration at the stage when the solution is concentrated, and requires special measures and crushing of aggregates as described in the publication.

Furthermore, it is necessary that the core is not soluble in the solvent, while the coating polymer material is soluble in the solvent. Therefore, there are significant limitations on the material of the core and the material of the coating polymer material. As another method, a coating method using a dispersion (mainly an aqueous dispersion) in which a polymer substance and a colorant are dispersed has been proposed. This method, like the method using a solvent, requires equipment for removing water and is disadvantageous in terms of cost. Also, it is technically difficult to avoid particle agglomeration at the stage when the dispersion is concentrated. Furthermore, it is necessary to disperse the core in water, and an auxiliary material such as an emulsifier is required to disperse the highly hydrophobic core. Generally, such an emulsifier is a hydrophilic substance and deteriorates triboelectric charging properties in a highly insulating toner. This has a particularly bad effect under high humidity conditions. Therefore, it is necessary to remove such emulsifiers, but it is technically difficult to remove them, so it is preferable not to use them.

Furthermore, another method has been proposed in which a powder of a polymer material and a coloring agent is melted by heating and coated. In such a method, as described in the text of the publication, the temperature is adjusted to be low enough to avoid thermal aggregation of the core as much as possible, and high enough to bond the polymer material that is the coating material. It is stated that this temperature adjustment is important. This is intended to prevent the core materials from fusing together due to heat, but
Because the toner needs to be melted by heat and/or pressure during the fixing process, thermoplastic resin is mainly used as the material for the core material. It happens. If the polymer substance is completely adhered to the particle surface of the core material, even if thermal melting of the core material occurs during heating during adhesion of the polymer material, the shape of the polymer material will cause the core i.D. Agglomeration can be prevented to some extent. However, it is difficult to prevent the core material particles from thermally agglomerating due to thermal melting of the core material when the coating substance is adhered to the public, and it is technically difficult to obtain a partially coated toner. Have difficulty.

In JP-A No. 61-210368, a binder resin and a coloring agent are dispersed on the surface of spherical particles using a mixer such as a Henschel mixer or a super mixer, and the softening point is lower than the softening point of the spherical particles and lower than the softening point of the binder resin. A method of immobilization by treatment at high temperatures has also been proposed. This method has a material limitation in that the binder resin is lower than the softening point of the spherical particles, and as shown in the examples, heat treatment at 110°C to 140°C for 10 minutes requires thermal aggregation and melting of the spherical particles. Avoiding this problem is technically difficult, and depending on the material used, it may be subject to thermal deterioration, so it cannot be said that the problem has been fully resolved yet.

As described above, there is a strong demand in the art for uniform dispersion of charge control agents into individual toner particles. As a solution to this problem, Japanese Patent Application Laid-Open No. 63-138358
The publication proposes a method in which charge control agent particles are mixed with toner base particles and impact force is applied to fix the charge control agent particles to the surface of the toner base particles. Although this method is excellent in terms of dispersing the charge control agent, although the charge control agent particles are physically implanted in the center direction on the surface of the base particle, there is no connection in the tangential direction. The charge control agent particles are likely to be detached from each other due to rubbing between the carrier, sleeve, and toner, resulting in a problem in terms of durability.

[Problems to be Solved by the Invention] An object of the present invention is to provide a toner manufacturing method that overcomes the problems associated with the toner manufacturing method described above.

An object of the present invention is to provide a method for producing toner that can be charged uniformly and stably.

[Means and effects for solving the problems] The present invention provides 100 parts by weight of colored particles A consisting of at least a binder resin and a colorant, a particle size ratio of 0.2 or less to the colored particles A, and an absolute amount of triboelectric charge. 8012 to 1010 parts by weight of charged Ni controllable particles having triboelectric properties with a value of 3 μc/g or more, and resin particles C1 to C1 having a particle size ratio of 0.2 or less to colored particles A.
30 parts by weight of the mixture is passed through an impact section having a minimum gap of 0.5 to 10 mm formed from a rotating piece and a fixed piece, or at least two types of rotating pieces, at an ambient temperature of 10 to 90°C. This is a method for producing a toner for developing an electrostatic image, characterized in that charge control particles B and resin particles C are simultaneously immobilized on the surface of colored particles A by mechanical impact at an impact portion.

The present invention will be described in detail below.

In the toner obtained by the production method of the present invention, the charge control agent or charge control agent is firmly fixed on the surface of the colored particles A by the combination of the resin particles C, and is present uniformly and stably in each toner particle. Therefore, the amount of triboelectric charge between toner particles becomes extremely uniform. On the other hand, if the charge control agent and the toner matrix are simply mixed uniformly, the charge control agent adhering to the toner surface will easily detach during the continuous copying process, contaminating the carrier or toner carrier, and causing damage to the toner. As a result, the amount of triboelectric charge gradually decreases, resulting in a decrease in image quality and an increase in fog, which is undesirable. Even in the case of toner produced through conventional melting, kneading, pulverizing, and classifying processes, some of the charge control agent tends to be detached due to its weak adhesion on the toner surface, and at the same time, it may damage the carrier or toner carrier. To contaminate. Furthermore, due to its function, the charge control agent only needs to be present on the surface of the toner, and what is present in the toner particles is substantially wasted. It is believed that in conventional toner production, only a portion of the added charge control agent is used and most of it is wasted. Also, it was difficult to control the amount of surface area.

In other words, there are differences in dispersibility depending on the crosstalk between the binder resin and charge control agent used and the kneading method.For example, lowering the kneading temperature may improve dispersibility, but cutting the binder resin or coloring it Since there is a tendency for the dispersibility of the agent to be poor, etc., it is not always the case that the preferred kneading method is adopted for the charge control agent.

As a result, the way the rupture occurs due to impact during crushing is different.
It is assumed that the amount of toner surface area changes.

In addition, in the case of toner obtained by the turbidity polymerization method, it is difficult to control the amount of charge control agent on the surface from the viewpoint of dispersibility, as in the case of toner obtained by cross-mixing and pulverization. Further, it is considered that only a part of the added charge control agent was used and most of it was wasted.

Particularly in such a method, some of the charge control agents, such as metal complex salts of nigrosine monoazo dyes, have the problem of inhibiting polymerization, which may make it difficult to use large amounts. In addition, hydrolyzable materials, those that are decomposed by monomers, and highly hydrophilic materials may lose charge controllability or broaden the particle size distribution.
In some cases, it is difficult to use because it generates microparticles. Capsule 1 whose surface is coated with a resinous substance
~ In the case of coating materials, a coating method using a resin solution is mainly used, and at the same time, it is not always technically easy to control a uniform surface due to problems such as uneven distribution of charge control agents or the same problems as mentioned above. .

Also, even in toners in which only the charge control agent is applied to the toner base particles by mechanical impact force, the charge control agent is detached during the continuous copying process, although this is better than when the charge control agent is simply mixed uniformly. This was easy to occur and there was a problem in terms of durability.

However, in insulating toner, it is important to adjust the amount of triboelectric charge to a constant value. In other words, one of the important characteristics of being able to obtain good images even under different environments, and to obtain good images that are as good as the initial image even during continuous image output, is friction 41 (: How to control the amount of electricity). It is in.

In general, improving the rise of frictional 11F electricity tends to increase its absolute amount, especially in low humidity environments.
Due to the excessive amount of charge, it becomes necessary to create a large electric field to transfer the toner to the image plane, which may place a burden on the system and risk discharge due to dielectric breakdown.

On the other hand, if the charging characteristics are suppressed, especially in high-temperature environments,
It takes time to build up a sufficient amount of charge, and it is not possible to eliminate l.ner, which is deposited on the outside of the latent image member by forces other than electrical forces, resulting in problems such as contamination of the image. These problems can be solved by partially immobilizing the charge controllable particles B on the surface of the colored particles A. That is, since the charge control agent is uniformly and partially present on the toner particles, the amount of triboelectric charging is controlled by the antistatic effect. On the other hand, if the charge controllable particles B are present entirely on the toner particles, it is estimated that the electrostatic effect is small and the absolute amount of triboelectric charge (absolute value of triboelectric charge) becomes too large.

The toner according to the present invention has charge-controllable particles in powder form that are firmly fixed together with resin particles by mechanical impact. Therefore, the toner treated according to the present invention can be used in subsequent steps, such as removal of silica, etc. The toner can be removed virtually without being released by stirring during addition, stirring during development, rubbing, etc.
It works in unison.

Since the amount of charge control agent on the toner surface is controlled by the amount added and is present uniformly, a uniform amount of triboelectric charge is always obtained even during continuous copying, resulting in constant image density and stable image quality. An image is obtained.

Further, since the toner according to the present invention allows the charge control agent to exist only on the surface of the toner, the amount added can be lower than the conventional method of 175 (for example, about 1710).

Furthermore, since the toner produced by the above method has a charge control agent fixed on the toner surface, carrier contamination and sleeve contamination are extremely unlikely to occur, and good development characteristics can be obtained.

The charge controllable particles B may be either particles consisting of a charge control substance alone or resin particles in which a charge control substance is dispersed in a resin.

Particles B or C and colored particles A preferably have a value of (average particle size of particles B or C/average particle size of particles A) of 0.2 or less. When the particle size ratio exceeds 0.2, it is difficult to uniformly immobilize particles B and particles C on the surface of colored particles A.

The charge control material in the present invention refers to a material that satisfies the following triboelectric properties. That is, 100 parts by weight of a charge control substance was added to 100 parts by weight of a bulk polymer of polystyrene resin (weight average molecular weight approximately 100,000 to 200,000) using a hot roll.
The mixture is sufficiently kneaded at 0 to 150° C. (for example, about 30 minutes to 1 hour), cooled, and then crushed and classified to prepare polystyrene particles containing a charge control substance having a main particle size of 10 μm. Approximately 5 g of prepared Borisdirene particles and 200
Carrier iron powder that is not coated with resin and has a main particle size of ~300 mesh (for example, EFV200 manufactured by Nippon Iron Powder Co., Ltd.)
/300) 95 g at 25°C, 50-60% R11
(7) After leaving it in the environment overnight, mix thoroughly in a polyethylene container with a capacity of about 200cc.
The amount of triboelectric charge is measured by the usual blow-off method using an aluminum cell with a 400 mesh screen. The amount of triboelectric charge measured by this method has an absolute value of 3 μc/g or more, particularly 7 μc/g or more.

As the charge control substance used in the toner of the present invention, a positive or negative charge control agent that is at least solid at a temperature of 20 to 90° C. is used.

(1) The following substances can be used to control the toner to be positively charged.

Nigrosine, azine dye containing an alkyl group having 2 to 1B carbon atoms (Japanese Patent Publication No. 1627/1983), basic dye [
For example, C,1, Basic Yellow 2 (C,I41
000), C,1, Basic Yellow 3, C,1, Basic Red 1 (C,1,45160), C,1
, Basiclet 9 (C, 1,42500) , C
, T Basic Violet 1 (C, 1,42535
), C,1, Basic Violet 3 (C,L4
2555), C, 1, Basic Violet 10
(C, 1, 45170), C, 1, Basic Violet 14 (C, 1, 42510), c, r Basic Blue 1 (C, 1, 42025), C, 1, Basic Blue 3 (C, 151005), C, 1, Basic Blue 5 (c, x, 42140), C, 1, Basic Blue (C, 1, 42595'), C,
1, Basic Blue 9 (C, 1, 52015),
C, 1, Basic Blue 24 (C, 1, 5203
0), C,1 Basic Blue 25 (C,1,5202
5), C1, Basic Blue 26 (C, 144045
), C,1, Basic Green 1 (C,1,420
40), C,1, Basic Green 4 (C,1,4
Lake pigments of these basic dyes, such as [2000) ], (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide) etc.), C, I Solvent Black 3 (
C, 1, 26150), Banza Yellow G (C, I
.

11680), C, 1, Mordrant Black 11, C
, 1, Pigment Black 1, benzylmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, or dialkyltin compounds such as dibutyl or dioctyl, dialkyltin borate compounds, guanidine derivatives, vinyl polymers containing amino groups, amino groups Polyamine resins such as condensation polymers containing

(2) The following substances can be used to control the negative chargeability of toner. Special Publication No. 41-20153, No. 43-275
96, No. 44-8397, and No. 45-28478. Tokuko Showa 5
Zn, ΔR, Go of salicylic acid, dialkyl salicylic acid, naphthoic acid, and dicarboxylic acid described in Japanese Patent Publication No. 5-42752, Japanese Patent Publication No. 5-42752, Japanese Patent Publication No. 5-42752, Japanese Patent Publication No. 5-73114, and Japanese Patent Publication No. 59-7385. , Cr
, metal complexes such as Fe, sulfonated copper phthalocyanine pigments.

Furthermore, the charge control substance used in the present invention must have little environmental dependence, be thermally stable, mechanically stable, and chemically stable. .

When the charge control substance is a resin, particles B are obtained by pulverizing the resin by a commonly known method. If necessary, preferred particles B may be obtained by classification. Particles B may also be obtained by heated spraying.

These particles B are 0.00 parts by weight per 100 parts by weight of colored particles A.
It is preferable to use 2 to 10 parts by weight. Usage amount is 0.
If the amount is less than 2 parts by weight, sufficient chargeability will not be imparted to the toner, and uniformity among the toners will not be maintained. Further, if the amount used exceeds 10 parts by weight, the absolute amount of triboelectric charge becomes too large, making it impossible to obtain an image with high image density.

As the resin used for particles C, toner binding substances can be used, such as monopolymers of polystyrene and its substituted products: styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, Styrenic copolymers such as styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene-acrylonitrile-indene copolymer, niacrylic resin, methacrylic resin, silicone resin,
Examples include polyester resin, furan resin, and epoxy resin. Preferred binding materials include crosslinked styrenic copolymers or polyesters. Examples of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
Monocarboxylic acids with double bonds such as 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Substituted products thereof, such as dicarboxylic acids having double bonds such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, etc. Compounds with possible double bonds are used, such as aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, etc., such as ethylene glycol diacrylate, ethylene glycol diacrylate, 1,3-butanediol dimethacrylate, etc. Divinyl compounds such as carboxylic acid ester divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone having two double bonds, and compounds having three or more vinyl groups are used alone or as a mixture.

The Tg of such a resin is preferably 50° C. or higher, preferably 55° C. or higher in terms of so-called prolagging properties for long-term storage.

These resin particles C are added in an amount of 1 part by weight per 100 parts by weight of colored particles A.
It is preferable to use it in an amount of up to 30 parts by weight. If the amount used is less than 1 part by weight, the charge control particles B will be difficult to adhere firmly to the colored particles A, resulting in insufficient durability as a toner.On the other hand, if the amount used exceeds 30 parts by weight, free resin Particles are likely to be generated, which may adversely affect the chargeability of the toner.

In producing these resin particles C, the constituent materials are thoroughly kneaded using a thermal kneader such as a hot roll, kneader, or extruder, and then obtained by mechanical crushing and classification, or the materials are mixed into a binder resin solution. A method of obtaining a toner by dispersing it and then spray drying it, or a method of obtaining a toner by mixing a predetermined material with the A-mer to constitute the binder resin, emulsifying it to form a suspension, and then polymerizing it. Each method can be applied, such as a legal toner manufacturing method.

Colored particles A can be obtained, for example, by the following method. Colored particles A obtained by the pulverization method are obtained by melt-kneading a mixture consisting of at least a binder resin, a coloring agent, and a release agent if necessary, and then pulverizing the mixture with a commonly known pulverizer after cooling, and if necessary, classifying the mixture to determine the particle size. Use the one with the same distribution. The volume average particle size of the colored particles A preferred as a developing toner is 2 to 20 μm.

Examples of binding materials for l-ner include monopolymers of polystyrene and its substituted products: styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers,
Styrenic copolymers such as styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Niacrylic resin, methacrylic resin, silicone resin, polyester resin, epoxy resin etc. can be used. Preferred binding materials include crosslinked styrenic copolymers or polyester resins. Examples of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, Methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate,
Monocarboxylic acids having double bonds such as acrylonitrile, methacrylonitrile, acrylamide, etc., or substituted products thereof, such as maleic acid, butyl maleate,
Vinyl monomers such as dicarboxylic acids having double bonds such as methyl maleate, dimethyl maleate, and substituted products thereof; and the like may be used alone or in combination of two or more. As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as divinylbenzene,
Aromatic divinyl compounds such as divinylnaphthalene, etc.
For example, carboxylic acid esters with two double bonds such as ethylene glycol diacrylate, ethylene glycol diacrylate, 1,3-butanediol dimethacrylate, etc., divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, etc. and a compound having three or more vinyl groups can be used alone or as a mixture.

Next, the colorant used in the colored particles A produced by the pulverization method will be described. To produce magnetic l·ner, magnetic particles are added. In this case, the magnetic particles also serve as a coloring agent. The magnetic particles that can be used in the present invention include substances that are magnetized when placed in a magnetic field, such as powders of ferromagnetic metals such as iron, cobalt, and nickel, or alloys such as magnetite, hematite, and ferrite. and compound powders. Magnetic particles having a particle size of 0.1 to 1 micron, preferably 0.1 to 0.5 micron are used. The content of these magnetic particles is 10 to 65% by weight based on the weight of the toner.
, preferably 20 to 60% by weight. Further, these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent or a dithane coupling agent, or an appropriate reactive resin. In this case, it depends on the surface area of the magnetic fine particles and the density of the hydroxyl groups present on the surface, or it is less than 5% by weight (preferably 0% by weight).
．． Sufficiently preferable dispersibility can be obtained with a treatment amount of 1 to 3% by weight).

The colored particles A produced by the polymerization method can be obtained, for example, by the method shown below, but are not limited thereto. A monomer system in which a polymerizable monomer, a colorant, a polymerization initiator, and if necessary a crosslinking agent, a charge control agent, a polar polymer, and other additives are uniformly dissolved or dispersed is added to an aqueous phase containing a suspension stabilizer ( (i.e., a continuous phase) and granulated and polymerized while stirring. Thereafter, the suspension stabilizer is removed, and the product is separated from the oven and dried.

It is particularly preferable to obtain the colored particles A by the suspension polymerization method described below because the particle size distribution is sharp.

Polymerizable monomers that can be used to form the colored particles A are monomers having a CH2-C< group as a reactive group, such as styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, Styrenes such as p-methoxystyrene and p-ethylstyrene and their conductors Niacrylic acid, methacrylic acid, maleic acid, maleic acid hafester: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate 12 and other α-methylene aliphatic monocarboxylic acid esters; acrylic Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylic acid esters: Monomers having a reactive double bond such as a vinyl group such as acrylic acid or methacrylic acid salt conductors such as acrylonitrile, methacrylonitrile, and acrylamide.

These may be used alone or in combination. A crosslinking agent may be used if necessary. As a crosslinking agent, divinylbenzene, divinylnaphthalene, dielene glycyl dimethacrylate, dielene glycyl dimethacrylate]
・etc. can be exemplified. The amount of the crosslinking agent added is usually 1 to 5 parts by weight per 100 parts by weight of the polymerizable monomer. Further, a small amount of a polymer of these polymerizable monomers may be added to the monomer composition. Among the monomers mentioned above, polymerized colored particles A produced from styrene, styrene having a substituent such as an alkyl group, or a mixed monomer of styrene and other monomers have excellent developability and durability. It is preferable if you take this into account.

Further, when the polymerizable monomer is polymerized by adding a polar polymer having a polar group, a polar copolymer, or a cyclized rubber as an additive during polymerization of the monomer, preferable polymers 1 to 2 can be obtained. The polar polymer, polar copolymer or cyclized rubber is preferably added in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, per 100 parts by weight of the polymerizable monomer. If it is less than 0.5 parts by weight, it is difficult to obtain a sufficient pseudocapsule structure, and if it is more than 50 parts by weight, the amount of polymerizable monomer is insufficient and the properties as a polymerized toner tend to deteriorate.

A polymerizable monomer composition containing a polar polymer, a polar copolymer, or a cyclized rubber is suspended in an aqueous phase of an aqueous medium in which a dispersant having an opposite charge to the polar polymer is dispersed, and polymerization is carried out. It is preferable to let That is, the cationic or anionic polymer, cationic or anionic copolymer, or anionic cyclized rubber contained in the polymerizable monomer composition contains oppositely charged anions dispersed in the aqueous medium. The cationic or cationic dispersant and the toner particle surface are electrostatically attracted to each other, and the dispersant covers the particle surface to prevent the particles from coalescing.
In addition to stabilizing the particles, the added polar polymer, polar copolymer, or cyclized rubber gathers on the surface layer of the particles, which forms a tree, forming a kind of shell-like shape, and the resulting particles form pseudo-capsules. Become. Since the relatively high molecular weight polar polymer, polar copolymer, or cyclized rubber gathered on the surface layer of the particles encapsulates a large amount of low softening point compounds inside the toner particles, the polymer particles of the present invention have blocking properties. Provides excellent developability and abrasion resistance (=J. Examples of polar polymers (including polar copolymers and cyclized rubbers) and reverse loading dispersants that can be used in the present invention are shown below. In addition, the polar polymer has a weight average molecular weight of 5,000 to 500 as measured by GPC.
,000 is preferably used because it dissolves well in the polymerizable l-mer and is durable.

(i) Examples of the cationic polymer include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate-1 and diethylaminoethyl acrylate, styrene and nitrogen-containing monomers, etc. I
There are copolymers with Li-forms and copolymers with styrene, unsaturated carboxylic acid esters, etc. and the nitrogen-containing monomer.

(ii) Examples of anionic polymers include polymers of nitrile monomers such as acrylonitrile, polymers of halogen-containing monomers such as vinyl chloride, polymers of unsaturated carboxylic acids such as acrylic acid, and polymers of unsaturated carboxylic acids such as acrylic acid. There are polymers of basic acids, polymers of anhydrides of unsaturated dibasic acids, and copolymers of styrene and the monomer.

The dispersant is preferably an inorganic fine powder that has the ability to stabilize the dispersion of the monomer composition particles in an aqueous medium and is sparingly soluble in water. The amount of the dispersant added to the aqueous medium is preferably 0.1 to 50% by weight (preferably 1 to 20% by weight) based on water.

(iii) As the anionic dispersant, Aerosil #
200. There are colloidal silicas such as #300 (manufactured by Nippon Aerosil Co., Ltd.).

(iv) Examples of the cationic dispersant include aluminum oxide, magnesium hydroxide, and fine hydrophilic positively charged silica powder such as aminoalkyl-modified colloidal silica treated with a coupling agent.

An anionic cyclized rubber may be used instead of the above-mentioned polar polymer or copolymer.

To produce the magnetically polymerized colored particles A, magnetic particles are added to the monomer composition. In this case, the magnetic particles also serve as a coloring agent. Magnetic particles that can be used in the present invention include:
A substance that is magnetized when placed in a magnetic field is used, such as powders of ferromagnetic metals such as iron, cobalt, and nickel, or powders of alloys and compounds such as magnetite and ferrite. The particle size is 0.05-5μ, preferably 0.05μ.
Magnetic fine particles having a diameter of 1 to 1 micron are used. The content of the magnetic particles is preferably 10 to 60% by weight, preferably 20 to 50% by weight, based on the weight of the toner. Further, these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent or a titanium coupling agent, or a suitable reactive resin. In this case, it depends on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, but it is less than 5% by weight (preferably 0.1 to 3.0% by weight).
Sufficient dispersibility in the polymerizable IIL polymer and low softening point compound can be obtained with a treatment amount of (% by weight), and the physical properties of the colored particles A are not adversely affected. As the coloring agent for the colored particles A, conventionally known pigments such as dyes, carbon black, and grafted carbon black in which the surface of carbon black is coated with a resin can be used. The colorant is 0.5 to 30% by weight based on the polymer and low softening point compound.
Contains. A charge control agent and a fluidity modifier may be added (internally added) to the toner as necessary.

In the suspension polymerization method, a monomer composition in which a colorant or additives added as necessary are uniformly dissolved and dispersed is
An aqueous medium containing ~50% by weight of a suspension stabilizer (e.g., a poorly soluble inorganic dispersant) (e.g., heated to a temperature of 5° C. or higher, preferably 10° C. to 30° C. or higher than the polymerization temperature). The mixture is dispersed using a conventional stirrer, homomixer, pomosizer, etc. Preferably, the particles of the dissolved or softened monomer composition are of the desired toner particle size, generally less than 30 microns (e.g., volume average particle size 0.1 to 20 microns).
The stirring speed, time and temperature of the aqueous medium are adjusted to have a magnitude of . Thereafter, the temperature of the aqueous medium is lowered to the polymerization temperature while stirring is performed to such an extent that sedimentation of the particles is prevented, so that this state is substantially maintained by the action of the dispersion stabilizer. The polymerization temperature is 50°C or higher, preferably 55 to 80°C,
Particularly preferably, the temperature is set at 60 to 75°C, and a substantially water-insoluble polymerization initiator is added while stirring to carry out polymerization. After the reaction is completed, the produced toner particles are collected and dried by an appropriate method such as washing, removal of the dispersion stabilizer, tFiA, decantation, centrifugation, etc. to obtain colored particles A that can be used in the present invention. . In the suspension polymerization method, 200 to 3000 parts by weight of water is usually used as an aqueous dispersion medium per 100 parts by weight of the polymerizable monomer and low softening point compound.

Alternatively, after heating and mixing, it is also possible to form fine particles in the molten state. Various conventionally known liquid particle removal methods can be applied. Namely, a single-fluid nozzle using pressure, a double-body nozzle using high-pressure airflow, and a disk atomizer using a rotating disk.
etc. may also be used.

The binder resin of the colored particles A used in the present invention preferably has a softening point of 90 to 150°C, particularly preferably 90 to 140°C, as measured by the following method when the fixing method is heat fixing.

Using a flow tester model CFT-500 (manufactured by Shimabara Seisakusho), about 1.0 to 1.5 g of a 60-mesh pass product is weighed as a sample, and this is pressurized for 1 minute at a load of loOkg/cm2 using a molding device. This pressurized sample is measured with a flow tester under the following conditions, and the temperature corresponding to 1/2 of the stroke difference between the start of outflow and the end of outflow is defined as the softening point.

(Left below) Measurement conditions RΔTE TEM'P 5. O07M ('
C1 minute) SET TEMP 50. ODEG
(t) MAX TEMP 200. O.D.
To EGINTEIIV8L 2
．． 5 DEGPRE) IFAT 300.
0 SEC (seconds) LOAD 50.0
KGF (kg) DIE (DIΔ) 0
．． 5MM (mm) DIE (LENG)
1.0 MMPLUNGER1, OCM2 (cm2) When used as a pressure fixing capsule toner, waxes such as polyethylene wax, oxidized polyethylene, paraffin, fatty acids, fatty acid esters, fatty acid amides, fatty acid metal salts, and higher alcohols; ethylene-acetic acid Vinyl resin, cyclized rubber, etc. can be used. After heating and mixing, it is also possible to form fine particles in the molten state. Various conventionally known liquid atomization methods can be applied. That is, a single-fluid nozzle using pressure, a double-body nozzle using high-temperature air flow, a disk atomizer using a rotating disk, etc. may be used. Alternatively, it may be melted by heating in a solvent and cooled to form fine particles. Here, it is also possible to use a dispersant while stirring. If necessary, it is preferable to remove the dispersant by washing with water, acid or alkali. Such a granulation method is preferable because spherical particles can be obtained.

Examples of capsule wall-forming substances include: Polystyrene, poly-α-methylstyrene, styrene-brobylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene- Methacrylic acid ester copolymers (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-acrylonitrile-acrylic Styrenic resins such as acid ester copolymers (unipolymers or copolymers containing styrene or styrene substitutes): rosin-modified maleic acid resins, epoxy resins, polyester resins, ionomer resins, ketone resins, xylene resins, etc. .

The capsule wall forming method is a method that dissolves the wall material or changes the solubility characteristics of the wall material in a solvent that does not substantially dissolve the core particles, such as a phase separation method that precipitates the wall material by dropping a poor solvent. is preferably used.

When uniformly immobilizing particles B and particles C on colored particles A, it is preferable that colored particles A be spherical particles with few protrusions in order to uniformly immobilize particles B and particles C.

Next, the method for manufacturing the toner of the present invention will be described in detail below.

The immobilization method according to the present invention includes a pretreatment step in which particles B and particles C are uniformly attached to colored particles A, and a step in which the attached particles B and particles C are immobilized on colored particles A by impact force. have.

In the pretreatment, the particles B and C are rubbed against the colored particles A while being stirred, and are caused to adhere to the colored particles A by electrostatic force (and van der Waals force). Generally, a mixer with high-speed stirring blades is used, but any mixer with mixing and dispersion functions may be used.

Figure 1 shows an example of a mixer with high-speed stirring blades, and the pretreatment is to ensure that colored particles A, particles B, and particles C are well dispersed, and that colored particles A are pulverized to the extent that they are destroyed. It is necessary that this is not actually done.

Therefore, although it is determined by the physical properties of the material, the pretreatment temperature for colored particles A, particles B, and particles C is preferably 0 to 50°C, preferably 15 to 35°C, and the blade tip peripheral speed is 5 to 50°C. ~50 m/sec, and the processing time is preferably about 1 minute to 1 hour.

When carrying out such pretreatment, since the temperature increases due to stirring, it is preferable to cool the inside of the tank by cooling with a jacket or by immersing cooling air.

This pretreatment equipment does not need to be a mixer with high-speed agitation blades, as long as it has dispersion and mixing functions and has a sufficiently long residence time. You can also use it by dropping it.

The next method is fixation, but in toner, it is not preferable for colored particles A, particles B, or particles C to be released, or for particles B or particles C that have been attached to be released again. That's preferable.

It is important to control the impact force within a range that does not crush the colored particles A and the temperature within a range that does not cause fusion and aggregation. Immobilization equipment for carrying out this method - for example, a pin mill with a recycling function and a large number of rotating pins (see Figure 4-1), a rotating blade or hammer (rotating piece) and a liner (fixed piece) A crusher with a recycling mechanism (Figures 2-1 and 3-1)
(see figure) is valid.

The circumferential speed of the tip of the rotating piece that enters the device is 30 to 150 m/
sec is preferred. The ambient temperature varies depending on the physical properties of colored particles A and particles B or C, but is preferably 20 to 90°C, preferably 30 to 70°C, and the residence time in the impact part is 0.02°C.
sec to 12 sec is preferable. In the case of a bottle mill, it is necessary to increase the concentration of powder. Figure 2-1 or Figure 3-1
In the type of device shown in the figure, the powder buried at 1A is collected near the liner by centrifugal force, so the latitude of the powder concentration is wide. The shortest gap between the bottle mills or between the blade or the hammer and the liner is preferably about 0.5 to 10 mm, and more preferably adjusted to 1 mm to 8 mm to obtain good results.

To explain in more detail with reference to FIG.
The dispersion blade 1 is introduced from
4 through the impact section 19 (Fig. 2-2) between the plate 15 and the liner 18, which rotates along the axis 4, through the outlet chamber 21,
It passes through the return path 22 and the blower 25 and circulates through the same circuit again. After the immobilization IA is completed, particles A including particles B and particles C are taken out from the product outlet 23.

Here, the powder consisting of particles A2, particles B, and particles C is subjected to an impact 4-1 immobilization treatment at the impact part 19 shown in FIG. It is. Here, if necessary, it is preferable to flow cooling water into the jacket 26 to adjust the ambient temperature. In FIG. 2-2, the gap a between the blade 15 and Riley 18 is the shortest gap, and the gap a between the blade 15 and Riley 18 is the shortest gap.
The space corresponding to 50 widths is the impact part.

FIG. 3-3 shows the positional relationship between the liner 29 of the immobilization device and the rotating rotor 31, and the shortest gap between the liner 29 and the rotor 31 is defined as the tip of the protrusion toward the inner periphery of the liner 29. This refers to the difference in the radius of two circles: the circumference 51 obtained by connecting the two circles, and the locus 52 of the protrusion of the rotor 31. The same applies when a plate or a hammer is used instead of the rotor 31.

FIG. 4-2 is a schematic diagram of a bottle entering a bottle mill type fixing device as seen from the front of the device, and the gap 55 between the fixed bottle 39 and the rotating bottle 54 is the shortest gap. In addition, 57
indicates the maximum gap, and 56 indicates the trajectory of the rotating bin 54.

The toner obtained by the production method of the present invention can be applied to a known dry electrostatic image development method. For example, magnetic toners can be used in two-component development methods such as cascade method, magnetic brush method, microtoning method, two-component C bias development method, conductive component development method, insulating component development method, and jumping development method. Powder cloud method and fur brush method: Non-magnetic component development method in which toner is held on a toner carrier by electrostatic force and transported to a developing section for development: It is applicable to an electric field curtain inkstone imaging method in which toner is conveyed to a developing section by an electric field curtain method and subjected to development.

[Example] The contents will be explained in detail below based on examples.

Note that all parts listed below are parts by weight.

Example 1 Colored Particles A The above formulation was heated to 70° C. and uniformly dispersed, and then 10 parts of an initiator [V-[101 (manufactured by Wako Pure Chemical Industries, Ltd.)] was added to prepare a monomer composition.

After uniformly dispersing 0.25 parts of silane coupling agent [KBE903 (manufactured by Shin-Etsu Silicone)] in 1200 nl of ion-exchanged water separately heated to 70°C, colloidal silica [Aerosil #200 (manufactured by Nippon Aerosil)] was added.
5g was added and further dispersed evenly, pH = 6 at IIcρ.
This was adjusted to form a dispersion medium system.

The above monomer composition was added to this dispersion medium system and stirred for 60 minutes at 7500 rpm in a TK homomixer under a nitrogen atmosphere to granulate monomer droplets, and then polymerized in 20 hours while stirring with a paddle stirring blade. completed. Thereafter, silica as a dispersant was removed by alkali treatment, followed by 7 filtration, washing with water, and drying to produce colored particles A.

The particle size of colored particles A was measured with a Coulter counter (aperture diameter 100μ), and the volume average diameter was 1O90μ.
It was m.

Particles C can be manufactured by a known method.

Specifically, ion-exchanged water at I°C and 1.5 g of sodium lauryl sulfate were added to a four-necked 2J2 flask equipped with a reflux device, and an acidic sodium carbonate solution was added in advance.
Adjusted to H10. 200m of styrene monomer in this system
1+ was added and vigorously stirred with a homomixer to emulsify. While continuing to flow nitrogen gas into the system at IR/min, the contents were heated to 75°C and after the temperature became constant,
1 g of potassium persulfate was added to initiate the polymerization reaction, which was continued for about 3 hours, and then the internal temperature was raised to 80° C. and heated for 1 hour to complete polymerization. The obtained latex was purified by dialysis and fi-embedding with an ion exchange resin to remove the activator and oligomer. The iris-emitting latex after treatment was dried using a spray dryer to obtain spherical polystyrene particles C having a volume average particle diameter of 0.3 μm.

Next, 1000 parts by weight of colored particles A, 60 parts by weight of particles C,
Furthermore, as particles B, di-tert-butylsalidylic acid,
10 parts of the metal complex was pretreated using the apparatus shown in FIG. 1 at a stirring blade circumferential speed of 30 m/sec for 2 minutes. Thereafter, using the apparatus shown in FIG. 2-1, the immobilization process was performed by recycling for 3 minutes at the shortest gap InIn+ and the circumferential speed of the rotating piece 60 m/sec. At this time, the ambient temperature inside the aircraft was 50.
It was °C.

To 100 parts by weight of the above toner, 0.8 parts of hydrophobized silica Tallanox 500 (Talco) was externally added, and 6 parts of this toner was mixed with 94 parts of magnetic particles made by coating ferrite particles with an average particle size of 50 μm with an acrylic resin. A developer was prepared by mixing. Using this developer, a continuous copying test of 20,000 sheets was carried out on a Canon CLC-1 at room temperature (23°C, 360°C).
%R11), low temperature and low humidity (15℃, 10%RH), and high temperature and high humidity (32.5℃, 585%R11), there was extremely little ground braking and toner scattering during durability and during replenishment. Good quality images with an image density of 1.3 or higher were stably obtained.

Example 2 Colored Particles A The above formulation was heated to 70°C using an ultrasonic disperser (RUS-300 manufactured by Nippon Seiki Seisakusho) at a frequency of 20 KIfz,
Carbon black was hydrophobized by dispersion at an output of 30 W for 15 minutes.

was added to the above treatment solution and uniformly dissolved or dispersed while heating to 70° C., and then 10 parts of an initiator [V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)] was added to prepare a monomer composition.

Colored particles A were then produced by adjusting the dispersion medium system, granulating and polymerizing in the same manner as in Example 1. The particle size of colored particles A was 98 μm in volume average size.

Next, 1000 parts of colored particles A, 0100 parts of particles obtained in Example 1, and further 6 parts of monoazo metal complex as particles B.
The pretreatment and fixation treatment were performed in the same manner as in Example 1.

A developer was prepared in the same manner as in Example 1, and 20,000 images were printed under three environments. Good quality images with an image density of 1.3 or higher were obtained, and there were no problems with durability. Ta.

Example 3 Colored Particles A C, T Pigment Blue 15+3 was added as a coloring agent to 100 parts of polyester resin obtained by condensing bisphenol A propylene oxide toy and fumaric acid.
After adding 5 parts and premixing with a Henschel mixer,
After melting and kneading with a Miki roll mill, pulverizing with a jet mill,
Further classification was performed to obtain colored particles A having an average particle size of 11.5 μm.

Particle C Using the same polyester resin as colored particles A, repeated jet mill grinding under cooling and further classification resulted in zero
．． Particles C having an average particle size of 2μ were obtained.

Next, 1000 parts of colored particles A, 0200 parts of particles, and further 8 parts of tert-butylsalicylic acid metal complex as particles B.
The pretreatment and fixation treatment were performed in the same manner as in Example 1.

A developer was prepared in the same manner as in Example 1, and 20,000 images were printed under three environments. Good quality images with an image density of 1.3 or higher were obtained, and there were no problems with durability. Ta.

Comparative Example In Example 1, fixing treatment and developer preparation were performed except for particles C.

Using this developer, we printed 20,000 images on Canon's CL [knee 1].
The decrease in image density was noticeable after 1,000 copies or more.

[Effects of the Invention] As described above, the toner according to the present invention has excellent environmental resistance and can provide high-quality copied images for a long period of time under any conditions.

[Brief explanation of drawings]

Figure 1 is a diagram schematically showing an example of a stirring device for pre-treating colored particles A and particles B, and Figure 2-1 is a diagram schematically showing an example of a stirring device for pre-treating colored particles A and particles B. Fig. 2-2 is a partially enlarged view of the apparatus shown in Fig. 2-1, and Fig. 3-1 shows colored particles A and particles B.
Fig. 3-2 and 3-3 are partial views of the apparatus shown in Fig. 3-1; The figure schematically shows an example of a pin mill type device for immobilizing particles B on colored particles A, and FIG. 4-2 shows a partial view of the device shown in FIG. 4-1. 1... Jacket 2... Stirring blade 3...
Motor 4...Lid 5...Base
6...Control board 7...Cylinder
8... Lid lock 9... Cylinder

Claims (1)

[Claims] (1) Colored particles A consisting of at least a binder resin and a colorant
100 parts by weight of charge-controllable particles B having a particle size ratio of 0.2 or less with respect to the colored particles A and having triboelectric charging characteristics with an absolute value of triboelectric charge of 3 μc/g or more. 0 parts by weight, and a mixture of 1 to 30 parts by weight of resin particles C having a particle size ratio of 0.2 or less to the colored particles A at an ambient temperature of 10 parts by weight.
The rotating piece and the fixed piece, or at least two
The colored particles A are passed through an impact section having a minimum gap of 0.5 to 10 mm formed from a rotating piece of seed, and the charge control particles B and resin particles C are simultaneously applied to the surface of the colored particles A by mechanical impact at the impact section. A method for producing a toner for developing an electrostatic image, characterized by fixation.