JPH0815902A - Capsulated toner and its production - Google Patents

Abstract

PURPOSE:To produce a capsulated toner excellent in fixability and having a sharp electrostatic charge distribution and low dependency on environment by sticking a polymer contg. a chlorine-contg. vinyl monomer as a monomeric component to the surfaces of capsulated particles capable of forming radicals. CONSTITUTION:A polymer contg. a chlorine-contg. vinyl monomer represented by formula I or II as a monomeric component is stuck to the surfaces of capsulated particles with a substance capable of forming radicals on the surfaces to produce the objective capsulated toner. In the formula I, R1 is H, Cl, C or 1-3C alkyl. In the formula II, X is-CH2-,-COO-,-O-or p-phenylene, R2 is H or 1-3C alkyl and each of R3-R5 is H or Cl. The chlorine-contg. vinyl monomer is, e.g. an olefin compd., a (meth)acrylic ester compd., a vinyl ether compd. or a vinyl ester compd.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventional negative charge control methods for capsule toners include a method of allowing polyacrylonitrile to exist on the capsule surface (see Japanese Patent Laid-Open No. 62-106474), a nitro group, a carboxyl group, a carbonyl group, a nitrile group. , A fluorine atom, a cyano group or the like as a charge control group is used to form a polymer chain on the outer shell surface by graft polymerization (JP-A-63-177145, JP-A-6-176145).
3-177147 and JP-A-63-177148) are proposed.

Further, as a toner in which a halogen compound is present on the surface of capsule toner particles, a method of containing a halogen in an outer shell resin (see JP-A-59-187346), an interface for forming an outer shell material A method for producing a capsule toner by using a fluorine atom-containing compound as one of the polymerizable monomers (see JP-A-60-126657),
A method in which a charge control group containing halogen is bound to the outer shell to impart chargeability (see Japanese Patent Laid-Open No. 61-120160), and a method in which a fluorine-containing vinyl monomer is attached to a capsule toner by graft polymerization (Japanese Patent Publication No. 3-22
No. 0561 and Japanese Patent Publication No. 5-19523) are proposed.

However, these encapsulated toners are less likely to be sharply charged, have poor fixability, have insufficient charge rise, and have poor environmental resistance.
That is, since the halogen-containing monomer is attached at the time of forming the outer shell, the strength of the outer shell is liable to be insufficient and the charge control group is apt to be biased.
As a result, the charge distribution became non-uniform, and it was not possible to impart sufficient chargeability to the toner. In addition, special fair 3-
The capsule toner using the fluorine-containing polymer described in JP-A-220561 and JP-B-5-19523 had a problem in fixing property. It is considered that this is because the surface tension of the fluorine-containing polymer is low and thus the contact property with paper is deteriorated.

[0005]

Therefore, the present invention solves the above problems, and provides an encapsulated toner having excellent fixability, sharp charge distribution, and excellent environmental resistance, and a method for producing the same. It is what

[0006]

The present invention has solved the above problems by adopting the following configuration. (1) A capsule toner comprising a capsule particle having a substance capable of generating a radical on at least the surface thereof and a polymer containing a chlorine-containing vinyl monomer as a monomer component attached thereto.

(2) A capsule toner comprising a polymer containing a chlorine-containing vinyl monomer represented by the following general formula (I) or general formula (II) as a monomer component.

[0008]

Embedded image

[0009]

[Chemical 4]

(Where X is --CH₂-, -COO-,-
R represents an OCO-, -O-, or p-phenylene group, and R
₁Is a hydrogen atom, a chlorine atom or an alkane having 1 to 3 carbon atoms.
R represents a kill group₂Has 1 to 3 hydrogen or carbon atoms
Represents an alkyl group of R,₃, R _Four, R_FiveIs a hydrogen atom or
A chlorine atom, at least one of which is a chlorine atom,
n and m show the integer of 0-19. )

(3) A capsule toner obtained by chemically bonding the polymer described in (2) above to the toner surface by a graft polymerization method.

(4) A monomer having a radical chain transfer group is graft-polymerized on the surface of toner particles, and then the above
(2) A method for producing a capsule toner, which comprises radical-polymerizing the chlorine-containing vinyl monomer described above or the monomer and another monomer copolymerizable with the monomer to form a film.

[0013]

The present invention will be described in detail below. In the present invention, the substance capable of generating a radical means, in the presence of a monomer radical or cerium (IV) ion, a substance capable of causing a hydrogen abstraction reaction or an addition reaction to generate a radical, specifically, a polyamide, Examples thereof include polymers such as polyurea, polyurethane, polyester, polyvinyl acetate, polyvinyl alcohol, cellulose, synthetic rubber, styrene, (meth) acrylic copolymer, epoxy resin, phenol resin, acrylic resin and mixtures thereof.

In the present invention, the polymer to be attached to the surface of the capsule particles having the substance capable of generating radicals on the surface thereof contains a chlorine-containing vinyl monomer as a monomer. As the chlorine-containing vinyl monomer used here, olefin compounds such as chloropropene, dichloropropene, trichloropropene, chlorobutene, and chloropentene; chloroethyl (meth) acrylate, dichloroethyl (meth) acrylate, trichloroethyl (meth) acrylate, chloro (Meth) acrylic acid ester compounds such as propyl (meth) acrylate, chlorobutyl (meth) acrylate, chlorophenyl (meth) acrylate; chloroethyl vinyl ether, chloropropyl vinyl ether, chlorobutyl vinyl ether,
Vinyl ether compounds such as chlorophenyl vinyl ether; vinyl ester compounds such as vinyl chloroacetate, vinyl dichloroacetate, vinyl trichloroacetate, vinyl chloropropionate and the like.

The above-mentioned polymer may be formed by using the above-mentioned chlorine-containing vinyl monomer alone, or may be formed by using another vinyl monomer copolymerizable with the above-mentioned monomer. Other vinyl monomers include methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth)
(Meth) acrylic acid esters such as 2-ethoxyethyl acrylate, glycidyl (meth) acrylate, phenyl (meth) acrylate; vinyl group-containing cyano compounds such as acrylonitrile, methacrylonitrile, cyanostyrene; vinyl formate, acetic acid Vinyl, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl caproate,
Fatty acid vinyl esters such as vinyl caprylate and vinyl stearate; vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether and phenyl vinyl ether; vinyl ketones such as methyl vinyl ketone and phenyl vinyl ketone; Examples thereof include vinyl aromatic compounds such as styrene, chlorostyrene, hydroxystyrene, and α-methylstyrene. Among the above vinyl monomers, it is preferable to select from an olefin compound monomer, a (meth) acrylic acid ester monomer, a vinyl ester compound monomer, and a vinyl ether compound monomer. Particularly, a (meth) acrylic acid ester monomer, a vinyl ester compound monomer, and a vinyl ether compound monomer are suitable.

The chlorine-containing vinyl monomer of the present invention is preferably present in an amount of 5 mol% or more, particularly 10 mol% or more, based on the total polymerization amount. If the content of the chlorine-containing vinyl monomer is less than 5 mol%, the chargeability will be deteriorated and a sufficient charge amount cannot be obtained. In the present invention, the amount of the polymer attached is 100 parts by weight of the encapsulated toner particles,
The range of 0.1 to 20 parts by weight is preferable.

The term "adhesion" in the present invention means that the polymer is attached by a physical or chemical method, and the polymer is not detached from the capsule surface when the developer is used. In the present invention, various methods can be adopted as a method for adhering the above-mentioned polymer to the surface of the toner particles. In particular, the polymer is grafted onto the surface of the toner particles so that the above-mentioned polymer is not detached from the toner surface. Those chemically bonded by a polymerization method or the like are preferable.

The method of graft polymerization is Ce
Using (IV) as a catalyst, on the surface of the capsule toner particles,
A method of redox polymerizing a chlorine-containing vinyl monomer or a chlorine-containing vinyl monomer and another monomer copolymerizable with the monomer, and a monomer having two or more radical chain transfer groups using Ce (IV) as a catalyst. After the graft polymerization, a radical-containing polymerization initiator such as a peroxide or an azo compound, or a redox-based polymerization initiator in which a peroxide and a reducing agent are combined is used, and a chlorine-containing vinyl monomer or a chlorine-containing vinyl monomer is used. A method of radically polymerizing a monomer and another monomer copolymerizable with the monomer is preferably used. [For the graft polymerization method using Ce (IV), see "Graft Polymerization and Its Applications" by Fumio Ide (published by Kobunshi Kogakukai)]

Examples of the radical polymerization initiator used in the above method include hydrogen peroxide, potassium persulfate, ammonium peroxodisulfate, alkyl hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, azo compound and the like. . As the redox-based polymerization initiator, a combination of a peroxide such as persulfate, hydrogen peroxide, hydroperoxide and various reducing agents, for example, hydrogen peroxide and ferrous salt, benzoyl peroxide and dimethylaniline. , Potassium persulfate, NaHSO _{3, and the} like.

Further, as the monomer having two or more radical chain transfer groups, poly (meth) alcohol of polyhydric alcohol is used.
Acrylates (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol dimethacrylate, etc., which are reaction products of acrylic acid and amine and have two or more acrylic groups), Polyvinyl alcohols of polyhydric alcohols (for example, ethylene glycol divinyl ether), polyvinyl esters of polyhydric carboxylic acids (for example, divinyl succinate, divinyl phthalate), aromatic compounds having two or more vinyl groups (for example, divinyl). Benzene, p-allyl styrene, etc.). The polymer chain obtained from the monomer having two or more radical chain transfer groups is preferably in the range of 0.05 to 10% by weight, particularly 0.2 to 3% by weight based on the toner body.

The average particle diameter of the capsule toner of the present invention is 4
-30 μm, preferably 6-18 μm is suitable. The resin constituting the outer wall of the capsule toner of the present invention,
Polyurea resin, polyurethane resin, polyamide resin,
A polyester resin, an epoxy resin, an epoxy urea resin, an epoxy urethane resin or the like can be preferably used, and among them, a polyurea resin and a polyurethane resin are used alone or in combination, or, It is preferable to use the epoxy urea resin and the epoxy urethane resin individually or to use a combination of both. It is desirable to change the thickness of the outer shell between the case of the capsule toner intended for pressure fixing and the case of the capsule toner intended for heat fixing, and the kind and / or composition ratio of the constituent components can be changed. .

The core substance of the encapsulated toner particles is composed mainly of a pressure-fixing component for the purpose of pressure fixing, and is mainly composed of the heat-fixing component for the purpose of heat fixing. The substance is composed. In particular, for the purpose of pressure fixing, the core substance is mainly used in combination with a binder resin and a high-boiling-point solvent which dissolves the binder resin and a colorant, or mainly in combination with a soft solid substance and a colorant. If necessary, magnetic powder may be added in place of the colorant, and additives such as silicone oil may be added to improve the fixability. Further, a high boiling point solvent which does not dissolve the binder resin can be added to the high boiling point solvent which dissolves the binder resin. In pressure fixing and heat fixing, it is desirable to change the type and / or composition ratio of the constituent components.

Examples of the colorant include inorganic pigments such as carbon black, red iron oxide, dark blue and titanium oxide, azo pigments such as fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine and para brown, copper phthalocyanine and metal-free phthalocyanine. And phthalocyanine pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, and dioxazine violet. It is also possible to use disperse dyes, oil-soluble dyes and the like.

Further, in the magnetic-component toner, all or part of the black colorant can be replaced with magnetic powder. As the magnetic powder, magnetite, ferrite, a simple metal such as cobalt, iron, nickel, or an alloy thereof can be used. The magnetic powder may be surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent or an oil-soluble surfactant, or the surface may be coated with an acrylic resin, a styrene resin, or an epoxy resin. . Further, the coloring agent and the magnetic powder charged as one component of the core substance may be present at the interface between the core and the outer shell or in the outer shell after the capsule formation.

As the binder resin used for the core substance, a known fixing resin can be used. Specifically, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, butyl poly (meth) acrylate, poly (meth)
(Meth) acrylic acid ester polymers such as 2-ethylhexyl acrylate and poly (meth) acrylic acid lauryl; copolymers of acrylic acid esters and methacrylic acid esters; styrene monomers and acrylic acid esters or methacrylic acid esters Copolymers of polyvinyl acetate, vinyl propionate, polyvinyl butyrate, ethylene-based polymers such as polyethylene and polypropylene, and copolymers thereof; styrene-ptadiene copolymers, styrene-isoprene copolymers, styrene-malein Styrene-based copolymers such as acid copolymers; polyvinyl ethers, polyvinyl ketones, polyesters, polyamides, polyurethanes, rubbers, epoxy resins, polyvinyl butyral, rosins,
Modified rosin, terpene resin, phenol resin and the like can be used alone or in combination. It is also possible to polymerize in the monomer state after the formation of the charged capsules to obtain a binder resin.

The soft solid substance used as the core substance of the pressure-fixing capsule toner may be of any type as long as it has flexibility and fixing property at room temperature, but Tg is -60. Polymers in the range of 5 ° C to 5 ° C, or
Mixtures of that polymer with other polymers are preferred.

As the high boiling point solvent for dissolving the binder resin,
An oily solvent having a boiling point of 140 ° C. or higher, preferably 160 ° C. or higher can be used. For example Moderm Plastics E
Plasticizers from ncyclopedia (1975-1976)
You may choose from those listed in. Further, it is disclosed as a core substance of a pressure fixing capsule toner (for example, JP-A-58-145964 and JP-A-63).
No. 163373), a solvent having a high boiling point may be selected.

Specifically, phthalic acid esters (eg diethyl phthalate, dibutyl phthalate), aliphatic dicarboxylic acid esters (eg diethyl malonate, dimethyl oxalate), phosphoric acid esters (eg tricresyl) Phosphate, trixylyl phosphate), citric acid esters (eg, o-acetyltriethyl citrate), benzoic acid esters (eg, butylbenzoate, hexylbenzoate), fatty acid esters (eg, hexadecylmyristate, dioctyl adipate, Linseed oil, castor oil, edible oil), alkylnaphthalenes (eg, methylnaphthalene, dimethylnaphthalene, monoisopropylnaphthalene, diisopropylnaphthalene), alkyldiphenyl ethers (eg, o-, m-, p-methyldiphenylether), high Amide compounds of fatty acids or aromatic sulfonic acids (e.g., N, N- dimethyl lauroyl amide, N-
Butylbenzenesulfonamide), trimellitic acid esters (eg, trioctyl trimellitate), diarylalkanes (eg, diarylmethane such as dimethylphenylphenylmethane, 1-phenyl-1-methylphenylethane, 1-dimethylphenyl) Examples thereof include diarylethane such as -1-phenylethane and 1-ethylphenyl-1-phenylethane), saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons and chlorinated paraffins.

In the encapsulated toner of the present invention, conductive fine particles may be added to the particle surface. The conductive fine particles have an electric resistivity of about 10 ⁸ Ωcm or less, preferably 10 ⁸ Ωcm or less.
^It can be less than ⁵ Ωcm. Among them, electron conductive fine particles whose electric conductivity is less dependent on humidity, for example, carbon fine powder such as carbon black and graphite; copper, gold,
Fine powder of metal such as silver; metal oxide such as zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, molybdenum oxide, iron oxide, tungsten oxide; or antimony Metal oxides doped with metals; further, composite oxides of these are preferred. Among these, carbon black, tin oxide, and titanium oxide are particularly preferable.

The particle size of these conductive fine particles is preferably 2 μm or less, and particularly preferably 0.5 μm or less. If the amount of the conductive fine particles added to the toner is too large, the toner will not be charged, and if it is too small, the charge distribution will not become sufficiently narrow. Preferably, the conductive particles are 0.01 to 5 parts by weight, preferably 0.0 to 100 parts by weight of the capsule particles.
It is in the range of 5 to 1 part by weight.

As a method for adhering the above-mentioned conductive fine particles to the surface of the capsule particles, the conductive fine particles may be added to the capsule toner particles and dry mixed with a V blender, a Henschel mixer, or the like. The conductive fine particles may be dispersed in the suspension, wet-mixed, and then dried by spray drying or oven drying to be attached.

In the present invention, although the encapsulation method is not particularly limited, an encapsulation method by an interfacial polymerization method, which can provide sufficient coating and has a good outer shell mechanical strength, is suitable. The production of capsules by the interfacial polymerization method,
A known method can be used. For example, as a method of containing one component in the core substance in the capsule, a method of preliminarily charging the other core substance component together with the low boiling point solvent and the shell-forming component in a polymer state to form the shell by interfacial polymerization, ,
After forming the outer shell by charging interfacial polymerization in the monomer state,
A method of polymerizing a monomer to form a core substance can be used (JP-A-57-179860 and JP-A-58-66).
948, JP-A-59-148066, 59.
-162562 gazette).

[0033]

[Example 1]

(Production of Capsule Particles) 30 g of polyisobutyl methacrylate (Mw = 16 × 10 ⁴ ) and ⁴⁰ g of styrene-n-butyl methacrylate copolymer (Mw = 6 × 10 ⁴ ) in a mixed solution of 60 g of dibutylnaphthalene and 60 g of ethyl acetate.
Was added and dissolved. Magnetic powder (made by Toda Kogyo, EP
T-1000) (120 g) was added, and the mixture was dispersed by a ball mill for 16 hours. Next, to 200 g of this dispersion, 30 g of isocyanate (Sumijour L, manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 24 g of ethyl acetate were added and thoroughly mixed. (This liquid is referred to as liquid A.) On the other hand, 200 g of ion-exchanged water was charged with hydroxypropyl methylcellulose (Metronose 65SH5 manufactured by Shin-Etsu Chemical Co., Ltd.).
0) 10 g was dissolved and cooled to 5 ° C. (This solution is referred to as solution B.)

The liquid B was stirred with an emulsifying machine (Auto Homo Mixer, manufactured by Tokushu Kika Kogyo Co., Ltd.), and the liquid A was slowly charged into the liquid to emulsify the liquid. Thus, an O / W emulsion in which the average particle size of the oil droplet particles in the emulsion was about 12 μm was obtained.
Next, instead of the emulsifier, a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller-type stirring blade was used.
Stirred at 00 rpm. After 10 minutes, 100 g of a 5% aqueous solution of diethylenetriamine was added dropwise thereto. After completion of the dropping, the mixture was heated to 60 ° C. and the encapsulation reaction was performed for 3 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated 7 more times to wash the capsule particles. In this way, capsule particles containing the oily binder were obtained. Ion-exchanged water was added to the capsule particles to prepare a suspension having a solid content concentration of 40%.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above-mentioned capsule particle suspension (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor). ) At 200 rpm. After adding 5 g of 1N nitric acid and 4 g of a 10% aqueous cerium sulfate solution, 1 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated twice more to wash the capsule particles. In this way, capsule particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the capsule shell were obtained.

The above-mentioned capsule particles were resuspended in ion-exchanged water and stirred at 200 rpm with a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor). Next, 0.4 g of potassium persulfate, 2
g of chloroethyl methacrylate and 0.16 g of sodium hydrogen sulfite were sequentially added, and the reaction was carried out at 20 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated four more times to wash the capsule particles. Thus, a capsule toner in which chloroethyl methacrylate was graft-copolymerized on the surface of the capsule shell was obtained. 0.15 g of carbon black (Regal 330 manufactured by Cabot Corporation) was added to the obtained capsule suspension.
R) The aqueous dispersion was added and mixed, poured into a stainless steel vat, and dried at 60 ° C. for 10 hours with a dryer (manufactured by Yamato Scientific Co., Ltd.).

(Evaluation Test) Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50% and the charge amount of the capsule toner was measured by a blow-off method, it was −18 μC / g, and the charge distribution was sharp. Similarly, when the charge amount of the capsule toner was measured by the blow-off method after mixing in an environment of temperature 28 ° C. and humidity 80%, it was −17 μC / g, and the charge distribution was sharp.

Next, with respect to this toner, a temperature of 20 ° C.
The image quality was evaluated under the environment of 50% humidity. The copying machine used was a Fuji Xerox 2700 modified for capsule toner, and a copy sample was obtained by the reversal development method. As a result, a good copy was obtained, and even if the obtained fixed image was rubbed with a finger, there was no stain on the background, and even if paper was placed on the fixed image and a letter was written on it with a ballpoint pen And showed very good fixability.

[Comparative Example 1] The same treatment as in Example 1 was carried out except that chloroethyl methacrylate in Example 1 was replaced with pentafluoropropyl methacrylate to obtain a capsule toner having pentafluoropropyl methacrylate on the surface of capsule particles. . Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50%, and the charge amount was measured by a blow-off method, it was found to be −19 μC /
The charge distribution was relatively sharp. Similarly, when mixed in an environment of a temperature of 28 ° C. and a humidity of 80% and measuring the charge amount of the capsule toner by the blow-off method,
The charge distribution was −18 μC / g, and the charge distribution was relatively sharp. However, when the image quality of this toner was evaluated in the environment of a temperature of 20 ° C. and a humidity of 50% in the same manner as in Example 1, the copy was good, but when the obtained fixed image was rubbed with a finger, the background was detected. Stain on the part, if you overlay paper on the fixed image and write on it with a ballpoint pen, back slipping will occur,
There was a problem with the fixability.

Example 2 (Production of Capsule Particles) 150 g of lauryl methacrylate monomer was added to polyisobutyl methacrylate (Mw = 1).
6 × 10 ⁴ ) 30 g was added and dissolved. Red pigment (Bayer, Hosta Palm Scarlet GO) 20 here
g was added and dispersed for 16 hours with a ball mill. Next, to 200 g of this dispersion, 10 g of isocyanate (Sumitomo Bayer Urethane Co., Sumidule L), 5 g of toluidine diisocyanate (Nihon Polyurethane Co., Coronate T) and 3 g of azobisvaleronitrile were added and mixed well. (This liquid is referred to as liquid A.) On the other hand, 250 g of ion-exchanged water was charged with hydroxypropylmethyl cellulose (Metronose 65SH5 manufactured by Shin-Etsu Chemical Co., Ltd.).
0) 10 g was dissolved and cooled to 5 ° C. (This solution is referred to as solution B.)

The liquid B was stirred with an emulsifier (manufactured by Tokushu Kika Kogyo Co., Ltd., Auto Hom Mixer), and the liquid A was slowly added to the liquid to emulsify it. Thus, an O / W emulsion in which the average particle size of the oil droplet particles in the emulsion was about 12 μm was obtained.
Next, using an agitator (three-one motor manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller-type agitating blade instead of the emulsifier, 4
Stirred at 00 rpm. After 10 minutes, 2.5% in this
100 g of the diethylenetriamine aqueous solution of was added dropwise. After completion of dropping, stirring was continued at room temperature to carry out a capsule reaction for 2 hours. Then, the reaction was carried out at 65 ° C. for 14 hours to polymerize the core substance. After completion of the reaction, pour into 2 liters of deionized water,
After sufficiently stirring, centrifugation was performed. After the capsule particles separated, the supernatant was removed. This operation was repeated five more times, followed by further washing with methanol. Thus, red capsule particles containing a soft solid substance were obtained. Ion-exchanged water was added to the capsule particles, and the solid content was 4
Prepared to 0% suspension.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above-mentioned capsule particle suspension (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd., three-one motor). At 200 rpm. After adding 5 g of 1N nitric acid and 4 g of a 10% aqueous cerium sulfate solution, 1 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and then centrifuged. After the capsule particles separated, the supernatant was removed. This operation was repeated twice more to wash the capsule particles. In this way, capsule particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the capsule shell were obtained.

The above-mentioned capsule particles were resuspended in ion-exchanged water and stirred at 200 rpm with a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor). Next, 0.4 g of potassium persulfate, 2 g
4-chloro-1-butene and 0.16 g of sodium bisulfite were sequentially added, and the reaction was carried out at 20 ° C. for 3 hours.
After completion of the reaction, the mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and then centrifuged. After the capsule particles separated, the supernatant was removed. This operation was repeated four more times to wash the capsule particles. In this way 4-chloro-
A capsule toner was obtained in which 1-butene was graft-copolymerized on the surface of the capsule shell. The obtained capsule suspension was placed in a stainless steel vat and dried at 60 ° C. for 10 hours with a dryer (manufactured by Yamato Scientific Co., Ltd.).

(Evaluation Test) Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50% and the charge amount of the capsule toner was measured by the blow-off method, it was −17 μC / g, and the charge distribution was relatively sharp. Similarly, when the charge amount of the capsule toner was measured by the blow-off method after mixing in an environment of a temperature of 28 ° C. and a humidity of 80%, it was −15 μC / g, and the charge distribution was relatively sharp. Next, regarding this toner, the temperature 2
The image quality was evaluated in the same manner as in Example 1 under the environment of 0 ° C. and 50% humidity. As a result, good copies were obtained. The obtained fixed image does not stain the background even if it is rubbed with a finger, and even if a sheet of paper is laid on the fixed image and a letter is written on it with a ball-point pen, there is no back flicker, and very good fixability is obtained. Indicated.

Comparative Example 2 4-chloro-1-of Example 2
Except for replacing butene with pentafluoropropyl methacrylate, the same treatment as in Example 2 was performed to obtain a capsule toner having pentafluoropropyl methacrylate on the surface of the capsule particles. Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50%, and the charge amount was measured by a blow-off method, it was −21 μC /
However, the charge distribution was very wide. Similarly,
The charge amount of the capsule toner was measured by the blow-off method after mixing in an environment of a temperature of 28 ° C. and a humidity of 80%.
Although it was 7 μC / g, it showed a very wide charge distribution.
Next, the image quality of this toner was evaluated in the same manner as in Example 2. As a result, a good copy was obtained. However, when the obtained fixed image was rubbed with a finger, the background portion was stained and paper was placed on the fixed image. When I used a ball-point pen to write letters on top of it, there was back slipping and the fixability was poor.

Example 3 (Preparation of Capsule Particles) 30 g of polyisobutyl methacrylate (Mw = 16 × 10 ⁴ ) and a styrene-n-butyl methacrylate copolymer (Mw =) were added to a mixed solution of 60 g of dibutylnaphthalene and 60 g of ethyl acetate. 6 x 10 ⁴ ) 40 g
Was added and dissolved. Magnetic powder (made by Toda Kogyo, EP
T-1000) (120 g) was added, and the mixture was dispersed by a ball mill for 16 hours. Next, to 200 g of this dispersion liquid, 20 g of isocyanate (Sumitomo Bayer Urethane Co., Sumidule L), 5 g of toluidine diisocyanate (Nihon Polyurethane Co., Coronate T) and epoxy resin (Epoxy Coat 801 manufactured by Yuka Shell Epoxy Co., Ltd.) 10 g
And 24 g of ethyl acetate were added and mixed well. (This liquid is referred to as liquid A.) On the other hand, 200 g of ion-exchanged water was charged with hydroxypropyl methylcellulose (Metronose 65SH5 manufactured by Shin-Etsu Chemical Co., Ltd.).
0) 10 g was dissolved and cooled to 5 ° C. (This solution is referred to as solution B.)

The liquid B was stirred with an emulsifier (manufactured by Tokushu Kika Kogyo Co., Ltd., Auto Homo Mixer), and the liquid A was slowly added to the liquid to emulsify it. Thus, an O / W emulsion in which the average particle size of the oil droplet particles in the emulsion was about 12 μm was obtained.
Next, in place of the emulsifier, a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor) was used.
Stirred at 0 rpm. After 10 minutes, 100 g of a 5% aqueous solution of diethylenetriamine was added dropwise thereto. After completion of dropping, the mixture was heated to 60 ° C. and the encapsulation reaction was performed for 3 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated 7 more times to wash the capsule particles. In this way, capsule particles containing the oily binder were obtained. Ion-exchanged water was added to the capsule particles to prepare a suspension having a solid content concentration of 40%.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above-mentioned capsule particle suspension (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Scientific Co., Ltd., three-one motor). At 200 rpm. After adding 5 g of 1N nitric acid and 4 g of a 10% aqueous cerium sulfate solution, 1 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated twice more to wash the capsule particles. In this way, capsule particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the capsule shell were obtained.

The above-mentioned capsule particles were resuspended in ion-exchanged water and stirred at 200 revolutions / minute with a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor). Next, in this, 0.4 g of potassium persulfate, 3 g
6-Chlorohexyl vinyl ether and 0.16 g of sodium hydrogen sulfite were sequentially added, and the reaction was carried out at 25 ° C for 3 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated four more times to wash the capsule particles. Thus, an encapsulated toner in which chlorohexyl vinyl ether was graft-copolymerized on the surface of the capsule shell was obtained. The resulting capsule suspension was spray dried to give 0.4 g of tin oxide.
A mixture of 0.3 g (manufactured by Mitsubishi Metals Co., Ltd.) and 0.3 g of hydrophobic silica (R972 manufactured by Nippon Aerosil Co., Ltd.) was added and mixed for 12 hours with a V blender (a transparent mixer manufactured by Tsutsui Rikagaku Kikai Co., Ltd.).

(Evaluation Test) Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50% and the charge amount of the capsule toner was measured by a blow-off method, it was −14 μC / g, and the charge distribution was sharp. Similarly, when the charge amount of the capsule toner was measured by the blow-off method after mixing in an environment of a temperature of 28 ° C. and a humidity of 80%, it was −12 μC / g, and the charge distribution was sharp. Next, the image quality of this toner was evaluated in the same manner as in Example 1 under the environment of a temperature of 20 ° C. and a humidity of 50%. As a result, good copies were obtained. Even if the obtained fixed image is rubbed with a finger, the background portion is not stained, and even if a sheet of paper is placed on the fixed image and a ballpoint pen is used to write on it, there is no back wandering. It was

Comparative Example 3 The same treatment as in Example 3 was carried out except that the chlorohexyl vinyl ether of Example 3 was replaced with acrylonitrile to obtain a capsule toner having hydrophobic silica on the surface of the capsule particles. 3 g of the obtained capsule toner and 100 g of an iron powder carrier whose surface was coated with a phenol resin were mixed in an environment of a temperature of 20 ° C. and a humidity of 50%, and the charge amount was measured by a blow-off method.
It showed a sharp charge distribution at 19 μC / g. Similarly, when mixed in an environment of a temperature of 28 ° C. and a humidity of 80% and measuring the charge amount of the capsule toner by a blow-off method,
A sharp charge distribution was shown at -9 μC / g. This toner greatly depends on the environment, and the charge amount of the toner is reduced under high temperature and high humidity.

Example 4 (Preparation of Capsule Particles) 30 g of polyisobutyl methacrylate (Mw = 16 × 10 ⁴ ) and a styrene-n-butyl methacrylate copolymer (Mw =) were added to a mixed solution of 60 g of dibutylnaphthalene and 60 g of ethyl acetate. 6 x 10 ⁴ ) 40 g
Was added and dissolved. Magnetic powder (made by Toda Kogyo, EPT
-1000) 120g was put, and it was made to disperse by a ball mill for 16 hours. Next, with respect to 200 g of this dispersion, 20 g of isocyanate (Sumitomo Bayer Urethane Co., Sumidule L), 5 g of toluidine diisocyanate (Nihon Polyurethane Co., Coronate T), epoxy resin (Epoxy Coat 801 made by Yuka Shell Epoxy Co., Ltd.) 10 g and 24 g of ethyl acetate were added and mixed well. (This liquid is referred to as liquid A.) On the other hand, 200 g of ion-exchanged water was charged with hydroxypropyl methylcellulose (Metronose 65SH5 manufactured by Shin-Etsu Chemical Co., Ltd.).
0) 10 g was dissolved and cooled to 5 ° C. (This liquid is B
Use as liquid. )

The liquid B was stirred with an emulsifying machine (auto homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.), and the liquid A was slowly added to the liquid to emulsify the liquid. Thus, an O / W emulsion in which the average particle size of the oil droplet particles in the emulsion was about 12 μm was obtained.
Next, in place of the emulsifier, a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor) was used.
Stirred at 0 rpm. After 10 minutes, 100 g of a 5% aqueous solution of diethylenetriamine was added dropwise thereto. After completion of dropping, the mixture was heated to 60 ° C. and the encapsulation reaction was performed for 3 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated 7 more times to wash the capsule particles. In this way, capsule particles containing the oily binder were obtained. Ion-exchanged water was added to the capsule particles to prepare a suspension having a solid content concentration of 40%.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above-mentioned capsule particle suspension (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd., three-one motor). At 200 rpm. After adding 5 g of 1N nitric acid and 4 g of a 10% aqueous cerium sulfate solution, 1 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated twice more to wash the capsule particles. In this way, capsule particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the capsule shell were obtained.

The above-mentioned capsule particles were resuspended again in ion-exchanged water and stirred at 200 rpm with a stirrer equipped with a propeller-type stirring blade (manufactured by Shinto Kagaku Co., Ltd., Three One Motor). Next, in this, 0.4 g of potassium persulfate, 3 g
3-chloro-2-methyl-1-propene, 0.16 g
Of sodium bisulfite were sequentially added and reacted at 25 ° C. for 3 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule particles settled, the supernatant was removed. This operation was repeated four more times to wash the capsule particles. In this way, a capsule toner in which 3-chloro-2-methyl-1-propene was graft-copolymerized on the surface of the capsule shell was obtained. The obtained capsule suspension was dried by spray drying, and further 0.4 g of tin oxide (S1, manufactured by Mitsubishi Metals) and 0.
A mixture of 3 g (manufactured by Nippon Aerosil Co., Ltd., R972) was added, and mixed with a V blender (manufactured by Tsutsui Rikagaku Kikai Co., Ltd., a transparent mixer) for 12 hours.

(Evaluation Test) Obtained Capsule Toner 3
Iron powder carrier 10 whose surface is coated with g and a phenol resin
When 0 g was mixed in an environment of a temperature of 20 ° C. and a humidity of 50% and the charge amount of the capsule toner was measured by a blow-off method, it was −18 μC / g, and the charge distribution was sharp. Similarly, when the charge amount of the capsule toner was measured by a blow-off method after mixing in an environment of a temperature of 28 ° C. and a humidity of 80%, it was −16 μC / g, and the charge distribution was sharp. Next, the image quality of this toner was evaluated in the same manner as in Example 1 under the environment of a temperature of 20 ° C. and a humidity of 50%. As a result, good copies without fog were obtained up to the 20,000th sheet.

Comparative Example 4 125 g of the capsule particle suspension prepared in Example 4 (corresponding to 50 g of capsule particles)
3 g of vinyl chloride resin was added and mixed with stirring. This was opened in a stainless steel vat and dried at 40 ° C. for 20 hours with a dryer (manufactured by Yamato Scientific Co., Ltd.). In this way, a capsule toner having a vinyl chloride resin on the surface of the capsule particles was obtained. Furthermore, a mixture of 0.4 g of tin oxide (manufactured by Mitsubishi Metals Co., Ltd., S1) and 0.3 g of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., R972) was added, and a V blender (manufactured by Tsutsui Rikagaku Kikai Co., Ltd., a transparent mixer) was added. And mixed for 12 hours. 3 g of the obtained capsule toner and 100 g of an iron powder carrier whose surface was coated with a phenol resin were used at a temperature of 20 ° C.
When mixed in an environment with a humidity of 50% and the charge amount was measured by the blow-off method, a sharp charge distribution was found at -12 μC / g. Similarly, when the charge amount of the capsule toner was measured by the blow-off method after mixing in an environment of a temperature of 28 ° C. and a humidity of 80%, a sharp charge distribution was found at −10 μC / g. Next, a copy sample of this toner was obtained in an environment of a temperature of 20 ° C. and a humidity of 50% in the same manner as in Example 4, and the image quality was evaluated. As a result, fog occurred from the 1000th sheet.

[0058]

EFFECTS OF THE INVENTION According to the present invention, by adopting the above-mentioned constitution, by adhering a polymer containing a chlorine-containing vinyl monomer as a monomer component to the capsule toner, the fixing property and the environmental stability of charging are improved. Thus, it becomes possible to provide a negatively chargeable toner having a sharp charge distribution, and as a result, a copy image having excellent image quality can be produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C08F 14/02 MKJ 14/06 MKB 16/24 MKZ 18/04 MLF 20/22 MMS 8619- 4J

Claims (4)

[Claims] 1. A capsule toner, wherein a polymer containing a chlorine-containing vinyl monomer as a monomer component is attached to the surface of capsule particles having a substance capable of generating radicals on at least the surface. 2. A formula represented by the following general formula (I) or general formula (II):
Contains chlorine-containing vinyl monomer as a monomer component
Encapsulating polymer
Na. [Chemical 1][Chemical 2](In the formula, X is -CH₂-, -COO-, -OCO-,-
R represents an O- or p-phenylene group, and R₁Is hydrogen
Child, chlorine atom or an alkyl group having 1 to 3 carbon atoms
Then R₂Is a hydrogen atom or an alkyl having 1 to 3 carbon atoms
Group, R₃, R _Four, R_FiveIs a hydrogen atom or a chlorine atom
At least one of them represents a chlorine atom, and n and m are
The integer of 0-19 is shown. ) 3. A capsule toner obtained by chemically bonding the polymer according to claim 2 to a toner surface by a graft polymerization method. 4. A monomer having a radical chain transfer group is graft-polymerized on the surface of the toner particle, and then the monomer is polymerized.
The chlorine-containing vinyl monomer described above, or with the monomer,
A method for producing a capsule toner, which comprises radical-polymerizing the monomer with another monomer copolymerizable with the monomer to form a film.