JP3347267B2 - Method for producing toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like.

[0002]

2. Description of the Related Art In recent years, as a method of developing an electrostatic charge image,
Technical development of the dry development method has been rapidly advanced. In the dry developing method, various methods are known as a method of fixing an image. In particular, a contact heat fixing method represented by a heat roller fixing machine is a non-contact heat fixing method such as a hot plate fixing device. It is excellent in that it has a higher thermal efficiency than that of the above, and in particular, can perform high-speed fixing and low-temperature fixing.

In the heating roller fixing method, a toner image obtained by development on an electrostatic recording medium (photosensitive drum) is temporarily transferred to a transfer sheet such as paper, and then the transfer sheet is transferred. The toner image is fused to a sheet by passing through a fixing roller for performing heat and pressure bonding, thereby performing fixing. However, when the toner is fixed by the heat roller fixing method using the conventional toner, the toner is brought into contact with the surface of the hot roll in a molten state, so that the toner adheres and transfers to the hot roll surface, and the next sheet to be fixed is fixed. However, there is a problem that this is re-transferred and soiled (offset phenomenon).

Generally, the toner for developing an electrostatic image is composed of a resin component, a colorant component composed of a pigment, a magnetic powder or a dye, and additional components such as a release agent and a charge control agent. For the purpose of ensuring the fixing at the fixing temperature, a low molecular weight polymer is contained in the binder resin for toner to lower the toner viscosity, and a part of the toner is supplied to the contact heating roller. For the purpose of preventing the offset phenomenon due to the adhesion of the toner, a method of increasing the toner elastic modulus by including a high molecular weight polymer in the binder resin for toner has been studied.

As a binder resin for a toner, which is a composite of a low molecular weight polymer and a high molecular weight polymer, a styrene resin is mainly used in many cases, and various polymerization methods have been studied. For example, Japanese Patent Application Laid-Open No. 2-48657 discloses that a high molecular weight polymer is produced by a suspension polymerization method using a polyfunctional initiator, and a low molecular weight polymer is produced in the presence of the high molecular weight polymer. We are studying the preparation of a coalesced polymer, drying the obtained polymer to obtain a solvent-free high-molecular weight and low-molecular weight polymer mixture, and using it as a binder resin for toner.

However, in general, when polymerizing by a suspension polymerization method, a high molecular weight polymer can be obtained relatively easily by using a crosslinking agent such as divinylbenzene, diethylene glycol dimethacrylate, and trimethylolpropane dimethacrylate. However, there are many problems at the stage of producing a low molecular weight compound. That is, in order to obtain a low molecular weight polymer by suspension polymerization, a large amount of chain transfer agent,
For example, it is necessary to use a mercaptan or a halogenated compound, and when a chain transfer agent is used, an undesired odor or a residual post-polymerization treatment is required in order to remove a residual halogenated compound. there were. Further, there is a problem that it is difficult to remove unreacted polymerizable monomers.

[0007] JP-A-2-48675 discloses that a low-molecular-weight polymer obtained by a solution polymerization method is dissolved in a polymerizable monomer for producing a high-molecular-weight polymer, and a polyfunctional (trifunctional) polymer is prepared. A technique has been disclosed in which a high molecular weight polymer is polymerized using an initiator to produce a resin for a toner. But,
The production of a high molecular weight resin by the solution polymerization method has a problem that the Weissenberg effect (the resin is wound around a stirring rod) is generated and the production is difficult. Further, US Pat. No. 5,084,368 discloses a method for obtaining a high molecular weight product by using bulk polymerization in combination with solution polymerization.

However, in any of the above-described production methods by solution polymerization, it is necessary to remove the solvent in order to obtain a solvent-free resin mixture, which is troublesome and costly. Furthermore, in the solution polymerization method, the weight average molecular weight is
It is difficult to produce a polymer having a high molecular weight of 200,000 or more, and it has not yet completely overcome the offset resistance.

Further, Japanese Patent Application Laid-Open No. 2-118583 discloses a technique for producing a toner for developing an electrostatic image by mixing, mixing and kneading a low molecular weight polymer, a high molecular weight polymer and a colorant. ing. However, in general, polymers having different molecular weights are largely different from each other, and polymers having different resin compositions have poor compatibility. Therefore, occurrence of offset property, which is a drawback of low molecular weight, and insufficient fixing at low temperature, which is a drawback of high molecular weight polymer, are repeated. It has the disadvantage that it occurs.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a binder resin component comprising a low-molecular-weight polymer, a high-molecular-weight polymer and a colorant which are uniformly compatible and dispersed, and have an offset resistance, a fixing property,
Efficiently and inexpensively produce an electrostatic image developing toner with low odor, which has good properties such as pulverizability during production, blocking resistance (non-aggregation property) during storage, and developability during image formation. It is to provide a method.

[0011]

According to the present invention, there is provided a resin emulsified dispersion composed of a resin emulsified dispersion and a colorant, and a solvent-free resin, which are mixed together, and heated in parallel or thereafter. To provide a method for producing a toner for developing an electrostatic charge image, comprising a step of producing a solvent-free colored resin mixture composition, and The resin composition is preferably a resin emulsified dispersion different from the resin composition of the solventless resin,
Solvent-free resin is preferably a polymer obtained by bulk polymerization, preferably the polymerization temperature of the bulk polymerization is 100 ° C. or higher, preferably a resin emulsion dispersion is an emulsion dispersion of the polymer obtained by emulsion polymerization, preferably The weight average molecular weight MW of the solvent-free resin is preferably 200,000 or less, preferably the weight average molecular weight of the resin of the resin emulsified dispersion is 50,000 or more,
The GPC molecular weight peak (Mp) of the resin in the resin emulsified dispersion is
Provided is a method for producing a toner for developing an electrostatic image, which is 300,000 to 3,000,000.

Thus, according to the present invention, a colored resin emulsified dispersion comprising a resin emulsified dispersion and a colorant, and a solventless resin are coexistent and subjected to a mixing treatment, and water is removed in parallel or thereafter. By performing the treatment to produce a solventless colored resin mixture composition and pulverizing the solventless colored resin mixture composition, it is possible to efficiently and inexpensively produce an electrostatic image developing toner. Further, when the electrostatic image developing toner is manufactured by the manufacturing method of the present invention, the low molecular weight polymer and the high molecular weight polymer are uniformly compatible and dispersed, non-offset properties, fixing properties, pulverizability at the time of manufacturing, It is excellent in blocking resistance (non-aggregation property) during storage, developability during image formation, and the like, and has remarkable characteristics that an electrostatic image developing toner with less odor can be produced. Hereinafter, the method for producing the electrostatic image developing toner of the present invention will be described in detail.

In the method for producing a toner for developing an electrostatic image of the present invention, a color resin emulsified dispersion comprising a resin emulsified dispersion and a colorant, and a solvent-free resin are coexistent and subjected to a mixing treatment.
A manufacturing method characterized by including a step of performing a water removal treatment in parallel or thereafter to manufacture a solventless colored resin mixture composition.

The method for producing the colored resin emulsified dispersion composed of the above resin emulsified dispersion and a colorant is not particularly limited as long as a colored resin emulsified dispersion can be obtained. For example, a method in which a resin emulsified dispersion and a colorant are mixed by a method such as stirring and kneading, a method in which emulsion polymerization is performed in an aqueous solution in which the colorant is dispersed, and the like can be mentioned, but a viewpoint that it is easily obtained From the viewpoint of mixing the emulsified resin dispersion and the colorant. The method of mixing is not particularly limited as long as it is a method of dispersing and mixing the resin emulsified dispersion and the colorant, and any method may be used.For example, a homogenizer, a sand mill and a resin emulsified dispersion may be used. , A disperser, a slasher, or another dispersing apparatus. The colorant mixed here may be in the form of a powder or may be dispersed in an aqueous medium in advance.

As a method of coexisting the above-mentioned colored resin emulsified dispersion and the above-mentioned solvent-free resin, and performing a mixing treatment and a water removing treatment, the colored resin emulsified dispersion and the solvent-free resin are mixed to remove water. There is no particular limitation as long as it is possible,
Either method may be used. For example, a method in which a colored resin emulsified dispersion and a solventless resin are added to an apparatus having a mixing function, a moisture removing function, and a melt kneading function to perform a mixing process and a moisture removing process Is mentioned. Examples of the device include a pressure kneader, a Banbury mixer, a roll mill, a single-screw continuous kneader, and a twin-screw continuous kneader.
A twin-screw continuous kneader is preferable in that the mixing and dehydration can be performed efficiently.

In these apparatuses, a colored resin emulsified dispersion is provided.
The solvent-free resin is added, and the mixing process is performed in a state where the water of the colored resin emulsified dispersion is present, and the dehydration process is performed in parallel with or after that. In the latter case, the device for performing the mixing process and the device for removing the water may be different devices, but in any case, the raw material addition, the mixing process, the water removing process, and the removal of the mixed resin composition are performed. Is preferably processed continuously.

The twin-screw continuous kneader has two rotating shafts to which a plurality of paddles are fixed, and the rotation of these rotating shafts continuously adds and mixes the raw material resin and moves the mixture at the same time. And a kneading machine capable of discharging the treated resin. In particular, a twin-screw continuous kneader in which the paddle rotates while being in contact with the body of the kneader and two paddles opposed to each other in contact with each other and rotate is preferable because the mixing effect is high.

FIG. 1 shows a preferred twin-screw continuous kneader. Two rotary shafts (2) each having a large number of paddles (1) fixed thereto are rotated by a motor (3), and this rotary motion is performed. Thereby, the resin is moved to the discharge port (5) while mixing the colored resin emulsified dispersion and the solvent-free resin continuously supplied from the input port (4). On the other hand, the water in the colored mixed resin composition is discharged from the evaporating port (7) by the heating jacket (6) heated by circulating the steam, and the uniformly mixed non-solvent colored resin composition having very little water content. You can get things. Increasing the opening area of the water evaporation port (7) makes it possible to remove water from the resin containing a large amount of water. The colored resin composition obtained from the discharge port (5) can be further continuously introduced into another processing device and processed into a pellet shape, a flake shape, or the like, depending on the intended use.

In the present invention, the resin emulsified dispersion mixed with the colorant is not particularly limited as long as the resin is dispersed in an emulsified state and the resin is dispersed in an emulsified state. Although it may be, for example, a resin emulsified dispersion obtained by forcibly emulsifying and dispersing a resin in water, a resin emulsified dispersion obtained by emulsion polymerization, and the like, but during storage and mixing with a solventless colorant-dispersed resin. From the viewpoint of stability, a resin emulsified dispersion obtained by emulsion polymerization is preferred.

The above resin emulsified dispersion is preferably used as a high molecular weight polymer component in the binder resin of the toner. In a resin emulsified dispersion used as a high molecular weight polymer component in a toner binder resin, the resin has a molecular weight of G
The molecular weight (molecular weight peak) Mp showing the maximum value in the PC measurement chart is preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000, and particularly preferably 600,000 to 1,000,000. If the Mp is less than the lower limit, the fixing property is good, but hot offset is apt to occur and the fixing temperature range is undesirably narrow. Further, the molecular weight of the resin used as the high molecular weight polymer component is preferably 50,000 or more, more preferably 100,000 or more, particularly preferably 300,000 or more, as represented by the weight average molecular weight Mw. If the Mw is less than the lower limit, the fixing property is good, but hot offset is apt to occur and the fixing temperature range is undesirably narrow.

The resin in the resin emulsified dispersion is not particularly limited as long as it is a resin used as a binder resin for the toner, and may be any resin, for example, an acrylic resin, a styrene resin, Epoxy resin, polyester resin, styrene butadiene resin and the like,
Styrene resins are preferred from the viewpoint that the performance as a toner is easily obtained.

The styrene resin is a (co) polymer having a styrene monomer as a main component. Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene. -Methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
pn-butylstyrene, p-tert-butylstyrene,
p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, Three,
Examples thereof include 4-dichlorostyrene, and among them, styrene is most preferable.

The other monomer that can be copolymerized with the styrene monomer is not particularly limited as long as it is a monomer that can be copolymerized with the styrene monomer. Is preferred. Examples of the acrylic monomer include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and nbutyl methacrylate. , Isobutyl methacrylate,
Examples include lauryl methacrylate and stearyl methacrylate, and particularly, n-butyl acrylate, ethylhexyl acrylate, n-butyl methacrylate, lauryl methacrylate, and the like. The acrylic component preferably has a glass transition temperature of a copolymer obtained by polymerizing the monomer of the styrene component with a monomer under ordinary conditions in the range of 40 to 80 ° C., more preferably glass. Transition temperature 50
Preferably it is in the range of ~ 70 ° C.

The particle size of the resin emulsified dispersion is 0.03 μm or more.
Preferably it is in the range of 1 μm. When the particle size of the resin emulsified dispersion exceeds 1 μm, the compatibility with the solventless resin is poor, and the obtained toner has poor fixability, and
Hot offset is likely to occur, and the fixing temperature range becomes narrow, which is not preferable. On the other hand, if the particle size of the resin emulsified dispersion is less than 0.03 μm, the amount of the emulsifier used for emulsion polymerization is increased, and the resistance of the obtained toner is undesirably reduced. In particular, the compatibility dispersibility between the solventless resin and the resin of the resin emulsified dispersion is related to the fixing property and durability of the toner,
Those having poor compatibility dispersibility are not preferable because so-called hot offset and cold offset occur simultaneously during fixing. In addition, those having poor compatibility and dispersibility tend to cause spent and fine particles of the toner, and have a short life of the developer.

When the above resin emulsified dispersion used as a high molecular weight polymer component in the toner binder resin is obtained by emulsion polymerization, a monomer, a water-soluble catalyst, an emulsifier and water as a polymerization medium are used. And the mixture is heated to the polymerization temperature. As the monomer, in addition to the monomer used for the polymerization of the solventless resin used as the low molecular weight polymer component, having two or more polymerizable double bonds,
Examples thereof include polyfunctional crosslinkable monomers, for example, divinylbenzene, aromatic divinyl compounds such as divinylnaphthalene, ethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, 1,3
Butanediol dimethacrylate, 1,6 hexanediol diacrylate, aryl methacrylate,
Diethylenic carboxylate, N, N divinylaniline, divinyl ether, divinyl sulfide and the like. Divinylbenzene, ethylene glycol dimethacrylate, and 1,6 hexanediol diacrylate are preferably used. The copolymerization ratio of the crosslinkable monomer is preferably 0 to 2% by weight of the monomers constituting the resin, more preferably 0.01 to 1% by weight,
Particularly preferably, those having a content of 0.02 to 0.8% by weight are suitably used.

When emulsion polymerization is carried out, most of the monomers are generally converted into polymers, and the amount of the remaining monomers is extremely small. However, if the residual monomer concentration is not sufficiently low for some applications, the residual monomer concentration may be determined, for example, by adding one or more initiators or reducing agents after polymerization, or by blowing steam or air. May be reduced.

When the above-mentioned initiator or reducing agent is added after polymerization, the concentration of the initiator or reducing agent is preferably 0.1 to 2.0 parts by weight based on 100 parts by weight of the total amount of the polymerizable monomer. Can be carried out by a method following a polymerization, a half-chain method or a continuous method using 0.5 to 1.0 part by weight. The feeding is carried out for 5 minutes to 5 hours, preferably 30 minutes to 4 hours, most preferably 1 hour to 3 hours.

If necessary, the pH may be adjusted with aqueous ammonia, an aqueous amine solution, an aqueous alkali hydroxide solution or the like. Such an emulsified dispersion usually has a solid content concentration of
Generally, the amount within the range of 10 to 70% by weight, preferably 20 to 60%, more preferably 30 to 50% is suitably used. Viscosity is usually 10,000 cps or less, (BH type rotational viscometer, 25 ° C, 2
0 rpm; the same applies to the following viscosity measurement conditions), and the pH is usually desirably in the range of 2 to 10.

The initiator that can be used in the above emulsion polymerization is any conventional water-soluble initiator. A group of suitable initiators are
Free radical initiators such as hydrogen peroxide, certain alkyl hydroperoxides, dialkyl peroxides, persulfates, bell esters, bell carbonates, ketone peroxides and azo initiators. Specific examples of suitable free radical initiators include hydrogen peroxide, t-butyl hydroperoxide, ammonium persulfate, potassium persulfate, sodium persulfate, tert.
-Amyl hydroperoxide, methyl ethyl ketone peroxide, 2,2'-azobis (2-amidinopropane), and 2,2'-azobis (4-cyanovaleric acid). The amount of free radical initiator used is
An amount of 0.03% to 1% based on the weight of the pre-monomer is preferred,
An amount of 0.05% to 0.8% is preferred, with 0.1 to 0.5% being particularly preferred.

A water-soluble redox initiator combining a water-soluble peroxide and a water-soluble reducing agent can also be used. As the peroxide used for the water-soluble redox initiator, the above-mentioned peroxides can be used, and as the reducing agent, sodium bisulfite, sodium pyrosulfite, sodium sulfite, hypophosphite, ascorbic acid, formaldehyde -Sodium sulfoxylate and the like can be used. The amount of peroxide used in the redox catalyst is in the range of 0.03 to 1% based on the total monomer weight. Further, in addition to the redox catalyst, a trace amount of a transfer metal, for example, ferrous sulfate,
Combinations of Mohr's salt copper sulfate and the like can also be used.

As the emulsifier used in the emulsion polymerization of the present invention, any of anionic emulsifier, nonionic emulsifier, cationic emulsifier and amphoteric emulsifier can be used, and these emulsifiers are used alone or in combination. be able to. Examples of the nonionic emulsifiers include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; and polyoxyethylene alkyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Ethylene alkylphenyl ethers; for example, higher sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; Riseraido, glycerin higher fatty acid esters such as monoglyceride stearate; for example, polyoxyethylene-polyoxypropylene block copolymers; can be exemplified, and the like.

Examples of the above-mentioned anionic emulsifiers include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate salts such as sodium lauryl sulfate; For example, poly (ethylene) alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; poly (ethylene) alkyl aryl ether sulfates such as sodium polyethoxyethylene nonyl phenyl ether sulfate; sodium monooctyl sulfosuccinate, dioctyl sulfosuccinate Alkyl sulfosuccinate salts such as sodium silicate, sodium polyethoxyethylene lauryl sulfosuccinate and derivatives thereof;
And the like.

Examples of the amphoteric emulsifier include alkyl betaines such as lauryl betaine. Further, a fluorine-based emulsifier in which at least a part of the hydrogen atom of the alkyl group of these emulsifiers has been substituted with fluorine can also be used. Examples of the cationic surfactant include octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dioctadecylsilylmethylammonium chloride, didodecyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, tetradecylbenzyldimethyl Ammonium chloride, octadecylbenzyldimethylammonium chloride, tetradecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, hexadecylbenzyldimethylammonium chloride, palmityltrimethylammonium chloride, oleyltrimethyl Nmo chloride, dipalmityl benzyltrimethylammonium chloride, dioleyl benzyltrimethylammonium chloride.

Coconut oil, balm oil, safflower oil,
Cottonseed oil, rapeseed oil, cationic emulsifiers starting from natural vegetable oils such as linseed oil can also be used.These cationic emulsifiers include coconut oil alkylbenzyldimethylammonium chloride, coconut oil alkyltrimethylammonium chloride, Examples of the amine acetate and hydrochloride include dodecylamine acetate, tetradodecylamine acetate, octadecylamine acetate, dodecylamine hydrochloride tetradecylamine hydrochloride, octadecylamine hydrochloride, and hardened tallowamine acetate. Further, reactive emulsifiers having a polymerizable double bond in the molecular structure can also be used. Examples of these reactive emulsifiers include reactive emulsifiers represented by the following general formulas (1) and (2). it can.

[0035]

Embedded image

[0036]

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Wherein R ¹ is independently hydrogen or a methyl group; R ² is an alkyl or alkenyl group having 6 to 18 carbon atoms;
Aryl group or an aralkyl group: EO is -CH ₂ CH ₂ O
X is a single bond or a methylene group; Z is hydrogen or SO ₃ M
Wherein M represents an alkali metal, ammonium or organic ammonium; m is a natural number from 1 to 50)

Among the reactive emulsifiers represented by the general formula (1), a specific example of the anionic reactive emulsifier wherein Z is SO3M is, for example, "Adecaria Soap SE-10N".
[Manufactured by Asahi Denka Kogyo Co., Ltd.]. Specific examples of the nonionic reactive emulsifier wherein Z is hydrogen include, for example, "Adecaria soap NE-10" and "Adecaria soap N".
E-20 "," Adecaria Soap NE-30 "and [made by Asahi Denka Kogyo Co., Ltd.].

Among the reactive emulsifiers represented by the general formula (1), specific examples of the anionic reactive emulsifier wherein Z is SO3M include, for example, "Aqualon HS-10", "Aqualon HS-20", [ Daikin Kogyo Co., Ltd.], and specific examples of the nonionic reactive emulsifier wherein Z is hydrogen include, for example, “AQUALON RN-10”, “AQUALON RN-20”, “AQUALON RN” -30 '', `` AQUARON RN-5
0 "and [these are manufactured by Daiichi Kogyo Co., Ltd.] and the like.

Examples of other anionic reactive emulsifiers such as “Latemul S-120”, “Latemul S-120A”,
`` Latemul S-180 '', `` Latemul S-180A '' (Kao
Alkyl sulfosuccinic acid alkenyl ether salt-based reactive emulsifier; for example, "Eleminol JS-2"
Alkyl sulfosuccinic acid alkenyl ester salt-based reactive emulsifier such as [manufactured by Sanyo Chemical Co., Ltd.]; for example, methylene bispolyoxyethylene alkylphenylalkenyl ether sulfate such as "ANTOX MS-60" [manufactured by Nippon Emulsifier Co., Ltd.] Ester salt-based reactive emulsifier; for example, "Latemul AS
K "(manufactured by Kao Corporation) or the like; an alkyl alkenyl succinate salt-based reactive emulsifier; for example," Eleminol RS-3 "
0 "[manufactured by Sanyo Chemical Co., Ltd.] and other polyoxyalkylene (meth) acrylate sulfate ester-based reactive emulsifiers; for example," RA-1120 "and" RA-2614 "[all manufactured by Nippon Emulsifier Co., Ltd.]
And polyoxyalkylene alkyl ether aliphatic unsaturated dicarboxylic acid ester-based reactive emulsifiers such as "ANTOX MS-2N" (manufactured by Nippon Emulsifier Co., Ltd.).
Acrylic acid sulfoalkyl ester salt-based reactive emulsifier;
Dihydroxyalkyl phthalate (meth) acrylate sulfate ester-based reactive emulsifier; for example, mono- or di (glycerol-1-alkylphenyl-3-allyl-2) such as "H-3330PL" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) -Polyoxyalkylene ether) phosphate ester-based reactive emulsifier;

Examples of nonionic reactive emulsifiers other than those described above include, for example, "RMA-564" and "RMA-568"
Co., Ltd.] and other polyoxyalkylene alkyl phenyl ether (meth) acrylate-based reactive emulsifiers; for example, polyoxyalkylene alkyl phenyl ether (meth) acrylates such as "RMA-1114" (manufactured by Nippon Emulsifier Co., Ltd.) A reactive emulsifier; and the like. The method for producing the high molecular weight polymer of the present invention is aqueous emulsion polymerization, but a water-soluble solvent such as alcohol may be used in combination.

Examples of the coloring agent include inorganic pigments, organic pigments and synthetic dyes. Inorganic pigments and organic pigments are preferably used, and one or more pigments and / or one or more pigments are used. Can be used in combination.

Examples of the above-mentioned inorganic pigments include metal powder pigments, metal oxide pigments, carbon pigments, sulfide pigments, chromate pigments, and ferrocyanide pigments.

Examples of the metal powder pigments include, for example,
Zinc powder, iron powder, copper powder and the like can be mentioned. Examples of the metal oxide pigments include magnetite, ferrite, red iron oxide, titanium oxide, zinc white, silica, chromium oxide, ultramarine, cobalt bull, celrian bull, Milanel violet, and lead tetroxide. Can be mentioned.

Examples of the above-mentioned carbon pigments include carbon black, thermotomic carbon, furnace black and the like. Examples of the sulfide pigment include zinc sulfide, cadmium red, selenium red, mercury sulfide, and cadmium yellow.

The above-mentioned chromate pigments include, for example,
Molybdenum red, barium yellow, strontium yellow, chrome yellow and the like can be mentioned. Examples of the ferrocyan compound pigments include, for example, miroribble.

Examples of the organic pigments include azo pigments, acid dye pigments and basic dye pigments, mordant dye pigments, phthalocyanine pigments, quinacdrine pigments and dioxane pigments. Examples of the azo pigments include, for example, benzidine yellow, benzidine orange, permanent red 4R, pyrazolone red, lithol red, and brilliant scarlet.
G, Bommarnlite and the like.

Examples of the acidic dye-based pigment and the basic dye-based pigment include Orange II, Acid Orange R,
Dyes such as eoxin, quinoline yellow, tartrazine yellow, acid green, peak blue, alkali blue, etc., precipitated with a precipitant, or
Dyes such as damine, magenta, makalite green, methyl violet, and victoria blue are precipitated with tannic acid, tartarite, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, and the like. .

Examples of the mordant dye-based pigments include metal salts of hydroxyanthraquinones and alizarinmer.
Drake and the like can be mentioned. Examples of the phthalocyanine pigment include phthalocyanine blue and sulfonated copper phthalocyanine. As the quinacridone pigment and dioxane pigment,
For example, quinacridone red, quinacridone violet, carbazole-dioxane violet and the like can be mentioned.

The above synthetic dyes include acridine dyes,
Aniline black, anthraquinone dye, azine dye, azo dye, azomethine dye, benzo and naphthoquinone dye, indigo dye, indophenol, indoaniline, indamine, leuco vat dye, naphthalimide dye, nigrosine, indulin, nitro and nitroso dye, oxazine And dioxazine dyes, oxidation dyes, phthalocyanine dyes, polymethine dyes, quinophthalone dyes, sulfur dyes, tri and diallyl methane dyes, thiazine dyes, xanthene dyes, and the like, preferably aniline black, nigrosine dyes, and azo dyes. It is preferably used as an azo dye having a salicylic acid, naphthoic acid or 8-oxyquinoline residue in a molecule among azo dyes, and forming a complex salt with a metal such as chromium, copper, cobalt, iron and aluminum. It is used. The amount of the colorant used is 30 to 1 based on 100 parts by weight of the solvent-free colored resin composition.
Part by weight is preferred, and 20 to 3 parts by weight is more preferred.

In the present invention, the solvent-free resin mixed with the colored resin emulsified dispersion includes flakes, powders, granules,
Block-like, molten resin, etc., the content of water or organic solvent is 10% by weight or less, preferably 5% by weight or less,
Particularly preferably, it means a resin containing substantially no water or organic solvent.

The solventless resin is used as a low molecular weight polymer component in the binder resin of the toner, and is preferably used in combination with a resin emulsified dispersion used as the high molecular weight polymer component.

The molecular weight of the solvent-free resin used as the low-molecular-weight polymer component in the toner binder resin is the molecular weight (molecular weight peak) Mp showing the maximum value in a measurement chart of gel permeation chromatography (GPC).
When represented by 1,500 to 30,000 is preferred, more preferably,
2,000 to 20,000. When Mp is less than the above lower limit, the fixability is good, but the toner easily aggregates in the developing machine and the life of the developer is short. Also, the storage stability of the toner is poor,
Hardens when stored at high temperatures. On the other hand, if Mp exceeds the above upper limit, spent and miniaturization hardly occur, but the fixability in a low temperature region becomes poor, the minimum fixing temperature rises, and
The offset / offset temperature is also poor, which is not preferable.

The weight average molecular weight MW of the resin used as the low molecular weight polymer component is preferably 1,000 to 200,000, more preferably 1,000 to 100,000; and particularly preferably 1,000 to 40,000. When the MW is less than the above lower limit, the fixability is good, but the toner is easily aggregated in the developing machine and the life of the developer is short. Further, the storage stability of the toner is poor, and the toner hardens during high-temperature storage. On the other hand, if the MW exceeds the above upper limit value, it is difficult to cause spent and miniaturization, but the fixability in a low temperature region is poor, the minimum fixing temperature is increased, and the cold offset temperature is also unfavorable.

The type of the solventless resin may be the same as the resin used as the high molecular weight polymer component in the toner binder resin.

The above-mentioned solventless resin used as a low molecular weight polymer component in the toner binder resin can be easily obtained by bulk polymerization. The bulk polymerization is carried out by coexisting the monomer and a catalyst that dissolves in the monomer, and heating the mixture to a polymerization temperature in a system in which substantially no solvent, dispersant, emulsifier, or the like is present. In addition, the raw material addition, the polymerization and the removal of the polymer may be continuously performed, but the bulk polymerization is continuously performed, and the above-mentioned colored resin emulsion dispersion is directly performed at a high temperature before cooling. Addition to a mixing device with a liquid is more preferable because the heat efficiency is good and the viscosity is reduced at a high temperature, so that mixing becomes easy.

The polymerization temperature of the bulk polymerization is preferably 130 to 250 ° C., more preferably 170 to 250 ° C., and particularly preferably 19 to 250 ° C.
0-230 ° C. If the reaction temperature is lower than the lower limit, the reaction rate is low, and the molecular weight peak Mp of the obtained polymer is undesirably high. If the reaction temperature exceeds the above upper limit temperature, a polymerization reaction and a decomposition reaction of the polymer occur, and an oligomer having a molecular weight of 500 or less increases. In addition, it tends to cause spent and miniaturization.

The catalyst used for the bulk polymerization can be any conventional oil-soluble initiator. A group of suitable initiators are
Examples include benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, and azobisisobutyronitrile. Particularly, since the reaction temperature is as high as 170 ° C. or more, preferable initiators include t-butyl hydroperoxide and di-t-butyl hydroperoxide. The amount of free radical initiator used is preferably 0.5%, more preferably 0.03% to 3%, more preferably 0.05% to 1%, based on the weight of the monomer.
% Amounts are particularly preferred.

The styrene type low molecular weight polymer obtained as described above has a conversion of 90% or more, preferably 95% or more.
More preferably, the reaction temperature and the reaction residence time are preferably set so as to obtain a conversion of 97% or more. If necessary, the residual monomer can be recovered by a thin film distillation apparatus or the like. The bulk polymerized low molecular weight polymer thus obtained is particularly preferred because it has a high toner chargeability and low odor.

When the solventless resin used as the low molecular weight polymer component and the resin emulsified dispersion used as the high molecular weight polymer component are combined to form a toner binder resin, The mixing ratio is 50 to 50%.
80 parts by weight, the resin of the resin emulsified dispersion is preferably in the range of 50 to 20 parts by weight, more preferably a solventless resin
55 to 75 parts by weight, and the resin of the resin emulsified dispersion is 45 to 25 parts by weight. When the mixing ratio of the solventless resin is less than the lower limit (the mixing ratio of the resin in the resin dispersion exceeds the upper limit), the anti-offset property is good, but the fixability in a low-temperature region becomes poor. , Undesirably increases the minimum fixing temperature.
When the mixing ratio of the solventless resin exceeds the above upper limit (the mixing ratio of the resin in the resin dispersion liquid is less than the above lower limit), the fixing property is good, but hot offset easily occurs, and the fixing temperature is high. The width is unfavorably reduced.

In the method for producing a toner for developing an electrostatic image of the present invention, a charge control agent and a release agent are used in a solventless dispersion resin, a colored resin emulsified dispersion, or a mixing treatment and a water removal treatment. Further, a toner additive other than a colorant such as a magnetic material can be blended.

Examples of the charge control agent include a nigrosine-based electron-donating dye for plus, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt, an alkylamide, a chelate, a pigment, and the like. Fluorinated activators and the like, and electron-accepting organic complexes for minus, other chlorinated paraffins, chlorinated polyesters, polyesters with excess acid groups,
Sulfonylamine of copper phthalocyanine and the like can be mentioned.

Examples of the release agent include Cd, Ba, Ni, Co, St, Cu, Mg, Ca salts of stearic acid, and oleic acid.
Zn, Mn, Fe, Co, Cu, Pb, Mg salt, Zn, C of palmitic acid
o, Cu, Mg, Si, Ca salts, Zn, Co, Ca salts of linoleic acid, Zn, Cd salts of ricinoleic acid, Pb salts of caprylic acid, Pb salts of caproic acid, Pb salts of caproic acid, etc. Salts and natural and synthetic paraffins and fatty acid esters or partially saponified products thereof,
There are alkylene bis fatty acid amides and the like, and one or a combination of two or more of these compounds is used as appropriate.

The colored resin mixture composition in the form of pellets, flakes or the like obtained by performing the mixing treatment and the water removal treatment as described above is cooled, then coarsely crushed, finely crushed by a jet mill or the like, By classifying with a classifier, an electrostatic image developing toner having a desired particle diameter can be obtained.

A generally used charge control agent, fluidizing agent and the like can be added to the above toner. Such a fluidizing agent is not particularly limited, and any fluidizing agent can be used. Examples thereof include fine powders of hydrophobic silica, titanium oxide, aluminum oxide and the like. Such a fluidizing agent is used in an amount of 0.0 to 100 parts by weight of toner.
It is preferable to add 1 to 5 parts by weight, more preferably 0.1 to 1 part by weight.

A carrier composed of iron powder or glass beads, preferably a carrier having a resin coating layer, is mixed with the toner produced as described above, and can be used as a two-component developer. Further, the present invention is not limited to the two-component developer alone, and is not limited to a one-component developer using a carrier, for example, a magnetic one-component toner containing a magnetic powder in the toner, and no magnetic powder in the toner. It can also be used as a non-magnetic one-component toner.

As a carrier having a resin coating layer, a carrier obtained by coating the surface of core particles made of iron, nickel, ferrite, or glass beads with a coating layer of an insulating resin is typical. As a resin material, generally, a fluorine resin, a silicone resin, an acrylic resin,
Styrene acrylic copolymer resin, polyester resin and polybutadiene resin are typical examples. When a developer containing the toner for developing an electrostatic charge image obtained by the present invention and a carrier having a resin coating layer as components is used, the spent particles which adhere to the toner particles on the surface of the carrier particles and are contaminated are extremely small. It is possible to control the triboelectric charging characteristics of the carrier and the toner, and is particularly suitable for a high-speed electrophotographic machine in that it has excellent durability and a long service life. Also,
Other styrene resin in addition to the main binding resin,
A polyester resin or the like may be blended and used, but the amount of the auxiliary binder resin in the total binder resin is preferably 30% by weight or less.

[0068]

EXAMPLES Each test method used in the following examples is described below. [Molecular Weight Measurement Method] The molecular weight at the peak position of the molecular weight distribution was determined by gel permeation chromatography (GPC).
Using an apparatus equipped with a column (manufactured by Tosoh Corporation: GMH × 3), the sample was treated with tetrahydrofuran (THF) in a volume of 0.1 mL.
The sample was dissolved at a concentration of 2 wt% and measured at a temperature of 20 ° C. at a flow rate of 1 ml / min. When measuring the molecular weight of a sample, a measurement condition in which the molecular weight of the sample is included in a range in which the logarithm of the molecular weight and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples are linear is used. Selected.

[Residual monomer measurement method] The residual monomer amount of each monomer was determined by measuring the sample in chloroform by gas chromatography (GC) using an apparatus equipped with a column (25% Thermo 1000). The extract was dissolved at a concentration of wt% and filtered, and 3 μl of the extract was injected to perform measurement. In measuring the concentration of the sample, the concentration was calculated from the calibration curve of each monomer.

[Blocking property] 24 hours in a 50 ° C constant temperature room.
After storing for a time, the degree of blocking of the powder was visually evaluated. ：: no blocking at all △: slightly blocking in cake form ×: hard blocking

[Resolution] The resolution was determined by copying the electrophotographic society test chart NO1-R1975, enlarging the resolution pattern 8.0 points by 100 times with an optical microscope, and visually observing as follows. 5. The fine lines are reproduced, and there is almost no fogging between the fine lines. 4. The fine lines are reproduced, but fog is slightly recognized between the fine lines. 3. Reproducibility of fine lines is rather poor, and there is also a lot of fogging between fine lines. 2. Reproduction of fine lines is poor, and there are many fogs between fine lines. 1. The thin line is not reproduced and is a single line.

[Fog concentration] ND-5 manufactured by JEOL Ltd.
The whiteness is measured using a 04DE colorimeter. Color difference L, a,
b is obtained and natural paper whiteness before printing K0 = 100-{(100-L) 2 + a2 + b2} 1/2 Non-image whiteness after printing K = 100-{(100-L) 2 + a2 From + b2} 1/2, the fog density is calculated by the following equation. Fogging density (%) = K / K0 × 100 The lower the fogging density, the better, the better at 0.3 or less.
If it is 5 or more, it can be judged as defective.

[Fixing Strength] The fixing strength is determined by the copying machine (SF-7).
300: manufactured by Sharp Corp.), a temperature sensor is attached, a black solid is fixed by a copier modified so that the fixing temperature can be changed, and the recording density is measured by a reflection densitometer RD-914. Gently apply a mending tape (Scotch Mending Tape 810) on the recording section where the density was recorded, and slowly apply a 1 kg cylindrical weight
Reciprocate. Thereafter, the mending tape is peeled at an angle of 180 degrees with respect to the recording surface, and the residual density is measured at the place where the recording density was measured before thinning. The fixing strength is calculated by the following equation. Fixing strength (%) = (residual density) / (initial density) × 10
0 The higher the fixing strength, the better, the better at 90% or more, 80%
The following can be judged as defective.

Example 1 (Preparation of solvent-free resin) In an autoclave equipped with a stirrer controlled at 220 ° C, a heating device and a cooling device, 100 parts by weight of styrene and 0.5 g of di-tert-butyl peroxide were added. Then, a monomer mixture obtained by uniformly mixing the mixed solution and the mixture by weight was continuously added in 30 minutes, and further kept at 220 ° C. for 30 minutes to obtain a solventless resin. The obtained solvent-free resin had a molecular weight peak Mp of 4,000 and a weight average molecular weight Mw of 4,600.

(Preparation of Resin Emulsion Dispersion) In a vessel equipped with a stirrer and a dropping pump, 27 parts by weight of deionized water and an anionic reactive emulsifier (Aqualon HS-10, trade name, manufactured by Asahi Denka Kogyo KK) 1 After charging by weight and dissolving with stirring,
A monomer mixture composed of 77 parts by weight of styrene, 23 parts by weight of butyl acrylate, and 0.05 part by weight of divinylbenzene was added dropwise with stirring to obtain a monomer emulsified dispersion.

Next, 120 parts by weight of deionized water was charged into a pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, and a dropping pump. After purging with nitrogen, the temperature was raised to 80 ° C. 5% by weight of the dispersion is added to the pressure-resistant reaction vessel, and 1 part by weight of a 2% by weight aqueous solution of potassium persulfate is further added.
Initial polymerization was performed at 80 ° C. After the completion of the initial polymerization, the temperature was raised to 85 ° C., and the remaining monomer emulsified dispersion and 4 parts by weight of 2% by weight potassium persulfate were added over 3 hours. A styrene resin emulsified dispersion having a solid content concentration of 0.2 μm and 40% was obtained. The obtained resin emulsified dispersion had a high polymerization conversion rate and could be polymerized stably. The resin emulsified dispersion was separated with an ultracentrifuge to separate the resin, and the molecular weight was analyzed. As a result, the weight average molecular weight Mw was 1,000,000.
0, the molecular weight peak Mp was 750,000.

(Preparation of Colored Resin Emulsion Dispersion) 135 parts by weight of the above resin emulsification dispersion, carbon black (trade name: carbon black MA-100S, manufactured by Mitsubishi Chemical Corporation) 8
Parts by weight, polypropylene wax (manufactured by Sanyo Chemical Co., Ltd.):
Viscol 550P (trade name) 2 parts by weight, nigrosine dye (Orient Chemical Co., Ltd .: Bontron N-01)
One part by weight was treated with a sand mill for 15 minutes to obtain a colored resin emulsified dispersion in which the colorant was uniformly dispersed.

(Adjustment of Toner) 100 parts by weight of the solventless resin and 146 parts by weight of the colorant-dispersed emulsified resin were mixed with each other in FIG.
Continuous kneader (Kurimoto Iron Works Co., Ltd .: KR)
C kneader), at a jacket temperature of 200 ° C., continuously mixing and heating to remove water, and the water content is 0.1%.
The following solventless colored resin mixture composition was obtained. The residual monomer content of the obtained solventless colored resin mixture composition is 120 pp.
m.

After cooling the solventless colored resin mixture composition,
It was crushed by a hammer mill and then finely crushed by a jet mill. Further, the obtained finely pulverized powder was classified by an air classifier to obtain particles of 5 to 20 μm, and 0.2 parts by weight of hydrophobic silica (trade name: R-972, manufactured by Nippon Aerosil Co., Ltd.) was added. The resulting mixture was mixed to obtain a toner having an average particle diameter of 10 μm. Using the toner and the silicone resin-coated carrier, a temperature sensor was attached to a fixing device of a copying machine (SF-7300: manufactured by Sharp Corporation), and a copying test was performed using a copying machine modified so that the fixing temperature could be changed. Fixing at 145 ° C
Even at 230 ° C., there was no stain due to offset of the toner on the heat fixing roll, and after copying 100,000 sheets, there was no toner spent on the carrier, and a clear image without stain fog was obtained as in the initial stage. . Other test results are shown in Table 1. All parts are parts by weight.

Example 2 (Preparation of solvent-free resin) Styrene 8 was used as a monomer mixture.
7 parts by weight, 13 parts by weight of butyl acrylate and 0.1 part by weight of di-tertiary butyl peroxide were mixed uniformly, except that the reaction temperature was 200 ° C. and the addition time was 30 minutes. Was carried out in the same manner as in Example 1. The molecular weight peak of the obtained solvent-free resin was 10,000
0, the weight average molecular weight was 13,000.

(Preparation of Resin Emulsion Dispersion) 70 parts by weight of styrene, 20 parts by weight of butyl acrylate, 10 parts by weight of butyl methacrylate and 0.1 part by weight of 1,6-hexanediol diacrylate Polymerization was carried out in the same manner as in Example 1 except that a monomer mixture of the above was used, and the emulsifier was changed to 1 part by weight of an anionic emulsifier (manufactured by Kao Corporation: Neogen R), to obtain a polymer having a weight average molecular weight of 850, 000,
A styrene resin emulsified dispersion having a molecular weight peak of 650,000, a particle diameter of 0.1 μm, and a solid content of 40% was obtained.

(Preparation of Colorant Aqueous Dispersion) Carbon Black (manufactured by Mitsubishi Chemical Corporation, trade name: Carbon Black MA-
100S) 8 parts by weight, an emulsifier (manufactured by Kao Corporation, trade name Neogen R) 0.5 part by weight, and deionized water 72 parts by weight are treated with a horizontal Glen Mill (manufactured by Asada Iron Works Co., Ltd .: trade name GMH-L). By doing so, a colorant aqueous dispersion was obtained.

(Preparation of Colored Resin Emulsion Dispersion) 107 parts by weight of the resin emulsification dispersion and 80 parts by weight of the aqueous colorant dispersion were treated with the horizontal Glen mill to obtain a color resin emulsification dispersion in which the colorant was uniformly dispersed. A liquid was obtained.

(Adjustment of Toner) 100 parts by weight of the solventless resin, 187 parts by weight of the colorant-dispersed emulsified resin, 2 parts by weight of polypropylene wax (trade name: Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.), and a nigrosine dye (Orient) 1 part by weight of Chemical Co., Ltd. (Bontron N-01) is mixed and heated to remove water in the same manner as in Example 1 to obtain a solventless colored resin mixed composition having a water content of 0.1% or less. Was.
The residual monomer content of the obtained solvent-free colored resin mixture composition was 90 ppm. After cooling the solventless colored resin mixture composition, a toner was obtained in the same manner as in Example 1, and a similar copy test was performed. As a result, it was possible to fix the image from 140 ° C. After copying 100,000 sheets, a clear image free of stain and fog was obtained as in the initial stage.

Example 3 (Adjustment of Toner) 100 parts by weight of the solvent-free resin prepared in Example 1 melted at 200 ° C. and 146 parts by weight of the colorant-dispersed emulsified resin prepared in Example 1 were rotated by two rotations. A twin-screw extruder equipped with a stirrer having a shaft, a heating jacket and a reduced-pressure moisture removing device (manufactured by Nippon Seisakusho Co., Ltd .: trade name TE)
In X), at a jacket temperature of 200 ° C., a mixing treatment and heating were performed to remove water, thereby obtaining a solventless colored resin mixed composition having a water content of 0.1% or less. The residual monomer content of the obtained solvent-free colored resin mixture composition was 135 ppm. After cooling the solventless colored resin mixture composition, a toner was obtained in the same manner as in Example 1, and a similar copy test was performed. As a result, it was possible to fix the image from 150 ° C. After copying 100,000 sheets, a clear image free of stain and fog was obtained as in the initial stage.

Comparative Example 1 (Preparation of Toner) The colored resin emulsified dispersion prepared in Example 1 was dried by a dryer at 105 ° C., and then crushed to about 1 mm by a hammer mill to disperse the colorant. 65 parts by weight of the high-molecular-weight polymer obtained and the solvent-free resin 100 prepared in Example 1.
A toner was obtained in the same manner as in Example 1 except that the continuous kneading machine used in Example 1 was used and the above-mentioned colorant-dispersed high molecular weight polymer was used. However, the fixing temperature was as high as 165 ° C., the offset to the heat-fixing roll was severe at 205 ° C., and the image quality obtained was fogged.

Comparative Example 2 (Preparation of Suspension Polymerization Dispersion) In a container equipped with a stirrer and a dropping pump, 200 parts by weight of deionized water and 1 part by weight of polyvinyl alcohol [manufactured by Kuraray Co., Ltd., trade name: PVA117] were added. After charging and stirring and dissolving, 77 parts by weight of styrene (St), 23 parts by weight of butyl acrylate (BA), and ditertiary butyl peroxyhexahydroterephthalate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayaester HTP) were added. Fifteen
A monomer mixture consisting of parts by weight was added, and the mixture was stirred to disperse the monomer mixture, and then heated to 90 ° C. to initiate polymerization,
Polymerization was performed for 2 hours to obtain a suspension polymerization resin dispersion. Next, the resin was separated from the suspension polymer resin dispersion and dried to obtain a suspension polymer resin. The average particle size of the obtained suspension polymerization resin is 180 μm, and the weight average molecular weight (MW) is 65.
The molecular weight peak (Mp) was 500,000.

(Preparation of colorant-mixed suspension polymerization resin) 54 parts by weight of the above suspension polymerization resin and carbon black (trade name: carbon black MA-100S, manufactured by Mitsubishi Chemical Corporation) 8
Parts by weight, polypropylene wax (manufactured by Sanyo Chemical Co., Ltd.):
Viscol 550P (trade name) 2 parts by weight, nigrosine dye (Orient Chemical Co., Ltd .: Bontron N-01)
One part by weight was uniformly mixed with a Henschel mixer (trade name: MITSUI HENSCHEL, manufactured by Mitsui Mining Co., Ltd.) to obtain a colorant-mixed suspension polymerization resin.

(Preparation of Toner) 65 parts by weight of the above-mentioned colorant-mixed suspension polymerization resin and 100 parts of the solvent-free resin prepared in Example 1
Parts by weight were treated in the same manner as in Example 1 to obtain a solventless colored resin mixture composition in which solventless coloring was dispersed. The residual monomer in the obtained solvent-free colored resin mixture composition was 930 ppm. A toner was obtained using the solventless colored resin described above in the same manner as in Example 1, and a similar copy test was performed. As a result, the fixable temperature was as high as 160 ° C., and the offset to the heat fixing roll was severe at 195 ° C., and The obtained image quality was also a lot of fog.

[0090]

According to the method for producing a toner for developing an electrostatic image of the present invention, a color resin emulsified dispersion comprising a resin emulsified dispersion and a colorant, and a solvent-free resin are coexistent and subjected to a mixing treatment. Or after that, performing a water removal treatment to produce a solventless colored resin mixture composition.

According to the present invention, a solventless colored resin composition uniformly mixed from a solventless resin and a colorant-dispersed emulsified resin comprising an emulsified dispersion of the resin and a colorant is obtained. By pulverizing, an electrostatic image developing toner can be efficiently and inexpensively manufactured. In addition, when the toner for developing an electrostatic image is manufactured by the manufacturing method of the present invention, the low molecular weight polymer, the high molecular weight polymer and the colorant are uniformly compatible and dispersed, non-offset properties, fixing properties, and pulverization during manufacturing. The toner has good properties, blocking resistance during storage (non-aggregation), developability during image formation, and the like, and can produce an electrostatic image developing toner with less odor.

[0092]

[Brief description of the drawings]

FIG. 1 is a preferred twin-screw continuous kneader for coexisting a colored resin emulsified dispersion composed of a resin emulsified dispersion and a colorant, and a solventless resin, and performing a mixing treatment and a water removing treatment. () Is a plan view thereof, and (b) is a side view thereof.

[Explanation of symbols]

 1. Paddle 2. Rotation axis 3. Motor 4. 4. Material input port 5. outlet for mixed product Heating jacket 7. Evaporation port

[Table 1]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-64-70765 (JP, A) JP-A-8-36272 (JP, A) JP-A-8-15909 (JP, A) JP-A-7-70 179505 (JP, A) JP-A-7-168392 (JP, A) JP-A-6-148937 (JP, A) JP-A-6-95433 (JP, A) JP-A-5-281780 (JP, A) JP-A-5-34978 (JP, A) JP-A-2-25971 (JP, A) JP-A-2-61650 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (12)

(57) [Claims] 1. A colored resin emulsified dispersion comprising a resin emulsified dispersion and a colorant, and a solvent-free resin coexistent and subjected to a mixing treatment, followed by heating in parallel or thereafter, followed by a water removal treatment, A method for producing a toner for developing electrostatic images, comprising a step of producing a solvent-free colored resin mixture composition. 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin composition in the resin emulsion dispersion is a resin emulsion dispersion different from the resin composition of the solventless resin. 3. The method for producing a toner for developing an electrostatic image according to claim 1, wherein the solvent-free resin is a polymer obtained by bulk polymerization. 4. The method according to claim 3, wherein the polymerization temperature of the bulk polymerization is 100 ° C. or higher. 5. The process for producing a toner for developing an electrostatic charge image according to claim 1, wherein said resin emulsion dispersion is an emulsion dispersion of a polymer obtained by emulsion polymerization. 6. The solvent-free resin having a weight average molecular weight MW of 200,
The method for producing a toner for electrostatic charge development according to any one of claims 1 to 5, which is not more than 000. 7. A method for producing a toner according to any one of the above resin emulsion dispersion of claim weight average molecular weight of the resin is 50,000 or more 1-6. 8. The resin emulsified dispersion according to claim 1, wherein the resin has a GPC molecular weight peak (Mp) of 300,000 to 3,000,000.
8. The method for producing a toner for developing an electrostatic image according to any one of items 7 to 7 . 9. The mixing process and the evaporative drying process method of manufacturing a toner according to any one of claims 1 to 8, made by biaxial continuous kneader. 10. The method for producing a toner for developing an electrostatic image according to claim 9 , wherein said twin-screw continuous kneader is provided with a heating jacket having a vapor chamber and / or an evaporating port on an upper part of a body. 11. The solventless resin and claims 1-10 or the <br/> manufacturing method of the electrostatic image developing toner according resin of the resin emulsion dispersion is styrene-based resin. 12. The total of the solvent-free resin and the resin emulsified dispersion.
Relative to 100 parts by weight, claim 1-1 said solventless resin is 50 to 80 parts by weight, the resin of the resin emulsion dispersion is 50 to 20 parts by weight
2. The method for producing a toner for developing an electrostatic image according to any one of 1 .