JPS61120160A - Microencapsulated toner - Google Patents

Abstract

PURPOSE:To enable electrostatic charge control and to eliminate fatigue deterioration by coating a core material with an outer shell chemically combined with a charge controlling group to obtain an encapsulated toner. CONSTITUTION:The core material contg. a fixing component is coated with the outer shell chemically combined with the charge controlling group. For example, the HORF, ClCO-R, R being alkyl, of the charge controller are reacted with the functional groups of the outer shell, such as -COOH, -OH, or -NH2, to chemically combine them, and a magnetic powder, a colorant, etc., are dispersed into a polyvinyl acetate resin, as the core material, and coated with the outer shell of a polyurethane resin, and xylenediamine is reacted with the resin of the outer shell to chemically combine them and form a microencapsulated toner. The use of the charge controlling group chemically combined with the outer shell permits the toner to be favorably controlled in charge, reduced in deterioration due to long-term uses, and a sharp image to be obtained.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a microcapsule type toner, and particularly relates to a microcapsule type toner whose charge is controlled by a novel method rather than by a method of adding a charge control agent.

[12! [US technology] Conventionally, as a dry electrophotography method, for example, US Patent No. 2,
No. 297,691 Akira I! , Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, etc., are known, but all of these methods uniformly apply charges on the photoconductive layer and A latent image is formed by irradiating the layer with a light image corresponding to the original, and then the latent image is developed with a black powder toner to become a visible image,
Copy onto paper as necessary: It is permanently fixed by heat, pressure, etc. The toner used in the process of developing a latent image has conventionally been made by dispersing a coloring agent such as carbon black in a binding resin such as polyethylene resin and pulverizing it into particles of about 1 to 30 μm. In the case of a two-component developer, such toner is used as a developer by being mixed with a carrier substance called a carrier such as iron powder or glass beads. The carrier and toner are triboelectrically charged with each other and have opposite polarities, and the toner is triboelectrically charged with the carrier and has a charge with a polarity opposite to that of the latent image. In addition, in the case of -component type developer, magnetic powder etc. are contained in F-chi particles,
Various studies have been conducted to control the charging of toner in order to charge it to a polarity opposite to that of the latent image by friction from a sleeve in a developing machine without using a carrier. For example, as a positive electrostatic control agent for toner, a method of adding an agent is commonly used.
JP-A-49-51951 discloses quaternary ammonium compounds, JP-A-51-11455 discloses triphenylmethane dyes, JP-A-52-113739 discloses tri-72-2-methane dye lake pigments, etc. Each of them has been disclosed, and as an arm electrostatic agent, #N@48-7893
Various metal-containing dyes are disclosed in Japanese Patent No. 7, No. 48-101939, No. 49-21151, No. 49-27729, No. 52-67331 and (/1q53-127726). No. 50-31828, 5
No. 0-68140, No. 52-104233 and Oka 54
-68637 specification and the like disclose various halogen compounds.

[l! 1. Problems that Ming attempts to solve] However,
Many of these compounds as charge control agents, especially dyes, are water-soluble, and many have ionized molecules, so their moisture resistance is lIj[, and the raw materials have low solubility, so it is difficult to control charge. In addition, adenoid-containing compounds have low solubility and dispersibility, resulting in non-uniform charging. Furthermore, toner resins are made with very limited physical properties required in terms of fixing properties and offset properties, so adding a charge control agent to them is a problem with the resin itself. Furthermore, since the triboelectric charging phenomenon occurs on the very surface of particles, a method of uniformly adding a charge control agent throughout the particles is unnecessary in itself, and is not necessary. Adding more than the above amount further deteriorates the physical properties of the resin and also places an additional load on the cost.In addition, in recent years, microcapsule type toners consisting of an outer wall and a core material have been developed. For example, regarding microcapsule type toner that can be fixed under pressure, various methods have been proposed.
No. 91724, No. 52-119937, No. 54-11
8249 and 55-84251 are known. For example, regarding microcapsule type toner for heat fixing, techniques described in Japanese Patent Application Laid-Open Nos. 58-174957, 58-178642, and 58-178843 are known. However, in each of these publications, there is no special description regarding the charging characteristics of the capsule type toner, and a charge control agent is externally added to the toner, for example, in the core material or outer wall, as in the case of ordinary toner. For this reason, it is not possible to properly control the charging characteristics of the toner, and when the charge control agent is exposed on the surface of the toner particles, the resistance of the toner particles decreases by 6 and the charging characteristics are lost. . As a result of extensive research in order to solve the above-mentioned problems, the present inventors discovered a completely new charge control means for a microcapsule type toner, and completed the present invention. [Means for Solving the Problems] The first object of the present invention is to control charge by a new method rather than the conventional method of adding a charge control agent. To provide a microcapsule type toner. A second object of the present invention is to provide a uniformly charged microcapsule toner. A third object of the present invention is to provide a microcapsule type toner in which the charge is controlled without changing the characteristics of the toner resin. This is achieved by a microcapsule type toner in which a charge control group is chemically bonded to the outer wall in a microcapsule type toner consisting of an outer wall that covers the surface of the particle. 0.2 μ, preferably 0.1 μ thick, and does not include the inside. In other words, the inventors have elucidated the surface triboelectric charging mechanism in the depth direction, and have found that up to this thickness is charged. In the present invention, a chemical bond refers to an ionic bond, a covalent bond, or any other chemical bond. Examples of methods for bonding to the surface of toner particles through chemical bonding include the following methods: For example, when forming microcapsules by chemical methods such as interfacial polymerization and 1 nsitu polymerization, at the same time a charge control method having a functional group is used. A chemical compound that can react with it
There is a method of chemically bonding the charge control group by reacting with the resin of the outer wall having the group. Alternatively, for example, a method in which a microelectronic polymer having an outer wall made of a functional polymer is first formed by the polymerization method described above, and then a charge control compound having a functional group is reacted to bond the charge control group to the surface of the outer wall. There is. Specific binding reactions of the above method are shown in Table 1. Table I Examples of compounds constituting the outer wall are listed below, but it goes without saying that the compounds are not limited thereto. [1] Examples of the resin having a carboxyl group as a functional group include acrylic acid, methacrylic acid, Polymers of unsaturated carboxylic acids such as maleic anhydride and copolymers of Kamishiro et al. and other vinyl monomers: Condensates of lysine and polyhydric acid hafides; Condensation systems such as polyamide 1@1 polyester resins Examples include polymeric compounds having a fog chain such as 14 molecules or a 1000H group at the end.Compounds having a charge control group that reacts with the Kaminokimiya functional group include noethanolamine, ethanolamine, CF,
OH, CF3CF! Oh. CHF! Alcohols containing a fluoro group such as CF -CH*OH; polyvalent aminated inclusions such as hexamethylenezamine, diethylenetriamine, xylylene quanmine, and phenylenediamine, etc. can be removed. [2] As a resin having an epoxy group as a functional group, polymers of furkyl and furkyl esters having an epoxy group of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl tutacrylate, and these and other vinyl monomers are used. copolymers with epoxy resins; examples include molecular compounds having epoxy groups in the main chain or at the end of noble chains, such as epoxy resins. Examples of compounds having IL control groups that react with the above-mentioned functional groups include hexamethylene triamine, diethylene triamine, xylylene amine, morpholine, 71-nylene amine, and 7-mino-compounds such as 71-nylene amine; Epoxy resin curing agents such as B-001, Ebikon Air T, Epiquier 7U, and Epiquier 103 (manufactured by Shell Yuka Epoxy Co., Ltd.); anhydrides such as hexahydro-7-talic anhydride, 7-talic anhydride, pyromellitic anhydride, etc. Examples include things. [3] As a resin having a hydroxyl group as a functional group,
Hydroxyethyl 7 acrylate, hydroxyethyl methacrylate, 2-human axypyl 7 acrylate, 2
- Polymers of acrylic acid or methacrylic acid esters having ester groups having 10H groups (hydroxyl groups), such as hydroxypropyl methacrylate, queethylene glycol monomethacrylate, propylene glycol monomethacrylate, propylene glycol monomethacrylate, and others. Copolymers with vinyl monomers; cellulose derivatives such as acetoxycellulose and ethylcellulose;
Examples include resins having 10H groups in side chains or terminals, such as epoxy wj11. Compounds having a charge control group that reacts with the above functional group include tele-7taloyl chloride, phenylmethane-4
, 4'-cyocyanate, toluylene diyinanate,
Examples include incyanate compounds such as phenyl isocyanate.・ [4] Examples of the resin having an amino group as a functional group include trimethyl7minoethyl7acrylate, trimethyl7minoethyl methacrylate, noethylaminoacrylate,
Copolymers with unsaturated carboxylic acid-containing amino ester polymers such as zoethyl 7-minomethacrylate, diptyl 7-minoethyl 7-acrylate, and other vinyl monomers; β-
Polymers of 7-minovinyl ethers such as 7-minoethyl vinyl ether and copolymers with other vinyl polymers; p
Polymers of styrene 7-mino derivatives such as -7-minostyrene, -17-minostyrene, p-yt tylaminostyrene, 3-styrene-β-alanine, 2-styrene/glumine, and copolymers with other vinyl polymers; Polymer layer of vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine Co-polymerization with vinyl monomer of VIK; Polymer of vinylamine derivatives such as 7lylamine and 7lylbennoramine or other polymers Copolymer with vinyl monomer; N-
Polymers of vinyl compounds having a heterocycle such as vinylcarbazole, vinylpyranone, vinylpyrazoline, vinylmorpholine, 2,4-yrmino-6-pinyru-3-trianone, vinylbipefuzone or copolymers with other vinyl monomers; Examples include polyamides such as 6-nylon and 6.6-nylon, nitrogen-containing molecules such as polyurea, polyurethane, and grease-resistant epoxy. Compounds having a charge control group that reacts with the above-mentioned functional groups include furkyl halide such as methyl fluoroguide, propyl bromide, and stearyl bromide; 7lyl halides such as chlorobenzene, iodobenzene, and iodotoluene; bromide; Halogen 7 reel such as 7 reel; Halogen compounds such as chlorine, bromine, iodine; Incyanate compounds such as phenyl isocyanate, xylene isocyanate, hexamethylene diisocyanate, phenylene noinanate, tonoley diisocyanate; acetic acid, perfluoroacetic acid, etc. Carvone t'**; acid anhydrides such as 7-talic anhydride, trinolitic anhydride; epichlorohydrin, butylene oxide, propylene. Examples include epoxy-containing compounds such as oxides. [5] Examples of the resin having a phenyl group as a functional group include styrene, a polymer of styrene derivatives such as a-methylstyrene, or a polymer of styrene derivatives with other vinyl monomers; phenyl acrylate, 11-phenyl methacrylate, Polymers of aromatic esters of acrylic acid or methacrylate such as benzyl acrylate and benzyl methacrylate; vinyl benzoate, vinyl p-phenylbenzoate, α-vinylnaphtonite, 0-vinylnaphtonite, vinyl heptalate, etc. Noyoshi! ) group vinyl esters and copolymers with other vinyl monomers; polymers of aromatic vinyl ethers such as phenyl vinyl ether and benzyl vinyl ether or copolymers with other vinyl monomers ; Aromatic vinyl ketone polymers such as phenyl vinyl ketone and benzurvinyl ketone or other vinyl ketone polymers or copolymers with other vinyl monomers; Aromatics such as polyethylene terephthalate and polybutylene terephthalate Examples include resins having an aromatic ring in the main chain or side chain, such as polyester, aromatic epoxy resin obtained from bisphenol A condensate, aromatic polyurea, aromatic polyurethane, and phenol formaldehyde condensate. Compounds having a cyanogen control group that reacts with the above functional groups include chlorine, bromine, fluorine, iodine, a reagent for the Derkuft reaction using diluted nitric acid, propyl chlorophyte, etc.; benzoyl chloride, etc. Friedel 7771 used
Examples include reaction reagents and the like. [6] Examples of resins having a herodene group as a functional group include vinyl chloride, vinylidene chloride polymers such as vinylidene chloride, or copolymers with other vinyl monomers; chloethyl acrylate; , acrylic acid such as c10-ethyl methacrylate, acryl-111-o-ly-C2Cl2g-nyl, 〇-ly-alophenyl methacrylate, polymers of alkyl halides or 7lyl esters of tu-acrylic acid, or other vinyl monomers. copolymer with polymer ho
-Kukustyrene, p-bromostyrene, 2-chloro-
Examples include halogenated styrene polymers such as 3,5-trimethylstyrene, 3-chloro-a-methylstyrene, a-C1a methylstyrene, and copolymers with other vinyl monomers. [7] Examples of resins having incyanate groups as functional groups include polyurethane-side LrK RIURE 7 resins, epoxyurea resins, and epoxyurethane resins, and these include, for example, the following polyvalent isocyanate-F compound compounds. Alternatively, it can be obtained by reacting an epoxy compound with a polyamine or polyol. I! 1. Polyvalent isone heptanate compounds include hexamethylene diisocyanate, a condensate of trimethicoolpropane and tolylene isocyanate, phenylene di-sifnate, tolylene neuson anate, nophenylmethano isocyanate. , crude diphenyl/tanisocyanate, 3,3'-cumethylno7
J! Examples include nylmethane-4,4'-twincyanate and triphenylnotane triisocyanate. As a commercially available product of the polyvalent isocyanate compound, "Sumiyel LJI"X manufactured by Sumitomo Bayer Urethane Co.
MI7Z-LE 44V-10J [x! pz-ru TJj
x Miku Ale HJr Desmono Ale RJ, Nippon Polyurethane Kogyo summer “Kone) EHJr Co a*-t LJr
"Millionate MT", "Millionate MRJ", etc.In addition, rPAPI 1 manufactured by Kasei 7 Fupnon Co., Ltd.
35JrPAPI 20Jr Isonet 125M
Jr Finne) 135LJ, rTDl 100JrT DI 80/21Jr manufactured by Mitsui Nisso Urethane Co., Ltd.
There are TDI 65/35J, etc. Next, as an epoxy compound, the reaction product of bisphenol A and epichlorohydrin is typical, and a commercially available bis7er7-el A type epoxy resin is "Epicor" manufactured by Yuka Shell Evo Toshi Co., Ltd. ) 801 Jr Epicote 81
5J r Epicoat 819J “Epicoat 8274
"Epicor) 828J "Epicor) 834J "Epicor) 152J rEpicor) 1904 [Epicor Y X -310J rEpicor) D X -
2554r Epicote 1045-A-704 and the like. Next, polyols and polyamines as reactants that react with the polyvalent incyanate compound or epoxy compound to form an outer wall include 1) polyols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, etc., glycerin; , trinothyrolepan, trinothyrolethane, 1,2.6-hexamethylene glycol, pentaerythritol, and others. 2) Polyamines Examples include ethylenenoamine, hexamethylenediamine, noethylenetriamine, iminobisbutylamine, phenylenediamine, kyrylenenoamine, triethylenetethumine, and cyclohexane. 3) In addition to the above polyols and polyols, water is preferably used. Compounds having a 1R control group that react with each of the polymers in item [7] above include ethanolamine, ethanolamine, and CF 30 H%cFscFzOH. CHF, CFtCF, CF20H, CHF, CFmaroCH
Alcohol having a fluoro group such as 10H, or hexamethylenezamine, xylylenecyamine, 7! Examples include aminated materials such as nylennoamine. Note that whether a toner is positively charged or negatively charged depends on the object to which it is frictionally charged! However, due to its stability,
Nitrogen-containing compounds are preferred for positive charge control, and fluorine-containing compounds are preferred for positive charge control. The resin having the Sakikifu philosophic group may be used alone or with other l1I
It is obtained by a mixture with N or by copolymerization with a monomer, and is used as a resin having physical properties suitable for the outer wall of a mic-a capsule type toner. Here, the above-mentioned resin is obtained from the specific monomers shown below, and is a copolymer of these monomers and the resin monomer having the above-mentioned functional group. In this case, the component of the resin having a functional group must be contained in the monopolymer or copolymer, or at least 0.1%, preferably at least 1%, in the total resin. However, a single product may be used as long as the physical properties of the resin are satisfied. Examples of monomers for obtaining a vinyl polymer as the resin having the functional group include, for example, styrene, vinyl acetate, vinyl tsupionate, vinyl penzoate, methyl acrylate, ethyl acrylate, and acrylic acid. There are n-butyl, methyl methacrylate, wrought chill methacrylate, paviru methacrylate, 1-butyl methacrylate, etc. The vinyl monomers of Niru et al. may be used alone or in combination of multiple monomers. It may be used as a copolymer. Monomers that provide polyester resins include terephthalic acid, isophthalic acid, 7y pinic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid,
Examples of diglycolic acid include ethylene glycol, diethylene glycol, 1,4-bis(2-human aQ diethyl)benzene,
1.4-Metal, propyl glycol, etc. can be mentioned. Caprolactam is used as a monomer for polyamide resin, and tribasic acids include terephthalic acid, isophthalic acid, anopic acid, maleic acid, succinic acid, sebacic acid,
Examples of diamines include thioglycolic acid and acid chlorides thereof, and examples of diamines include ethylenediamine, noaminoethyl ether, 1,4-noaminobenzene, and
．． Examples include 4-noaminobutane. As monomers for providing polyurethane resins, examples of cycloisocyanates include -phenylenenoisocyanate), p
Examples of glycols include silylene noisocyanate, 1,4-te) fumethylene diisonanate, and the like. Examples of glycols include ethylene glycol, diethylene glycol, and pucbylene glycol. Examples of monomers that provide polyurea resins include p-phenylene noisocyanate, p-xylylene noisocyanate) and 1,4-tetramethylene diisocyanate in the neuisocyanate order, and diamines include is ethylenenoamine, yaminoethyl ether, 1
*4-Noaminobenzene, 1"', 4-noaminobutane, etc. can be mentioned. Examples of amines used as monomers to provide epoxy resin include ethylamine, butylamine 1, ethylenediamine,
1,4-noaminobenzene, 1,4-noaminobutane,
Monoethanolamine and the like can be mentioned, and examples of the noeboxies include noglycidyl ether, ethylene glycol diglycinole ether, bisphenol A glycityl ether, and hyde a quinone noglycidyl ether. The above monomers may be used alone, but self-polymerizable monomers and other monomers may be used in combination. The outer wall obtained from the above polymerizable monomers and the reactive outer wall may be formed by crosslinking polymerization. This aggregate polymer may be a polymer that undergoes self-crosslinking polymerization, such as a prepolymer (in this case, the monomer that undergoes self-crosslinking polymerization may be used in combination with other monomers).
It may also be a cross-polymer formed by a cross-linking agent present during the polymerization of monomers. Any crosslinking agent can be used as long as it can cause steel bridge polymerization of the monomer used. Specifically, novinylbenzene, novinylnaphthalene,
Ethylene glycol dimethacrylate, Nosf Lengelicol Tsuno! Cleary),) 17/Tyrolpropane triacrylate! Compounds with two vinyl groups and compounds with three or more vinyl groups: Trivalent or higher alcohols such as glycerin, trino+propane, pentaerythritol; Trivalent or higher valent alcohols such as trimellitic acid, pyromellitic acid, etc. Carvone 1ljI and the like are used as crosslinking agents in the present invention. Therefore, the amount of crosslinking agent added to the monomer is o,
oos~20 heavy view%, preferably 1 of O01~5 heavy view%
IIN is preferred. Furthermore, as the core material in the Microphone, a II pushel type toner used in the present invention, when used as a pressure fixing toner, a base material mainly containing a pressure fixing component is used, and when used as a heat fixing toner, a base material mainly containing a pressure fixing component is used. A base material mainly containing a heat fixing component is used. For example, the pressure fixing component includes liquid polybutene, anopic acid group polyester,
Liquid polyester, butyl 7 tallate, quoctyl 7
Plasticizers such as tallate and chlorinated paraffin, unsaturated aliphatic esters such as linoleic acid, lylunic acid, oleic acid, and elitusnic acid, 7 sesame oil, eno oil, tung oil, L mustard oil, and field test of hemp oil. % Kapok oil, Ken Jiken, sesame oil, rice bran oil, soybean oil, soybean oil, corn oil, rapeseed oil, sunflower oil, corn oil, vegetable oils such as olive oil, squid oil, sardine oil, saury Oil, whale oil, beef tallow, lard, mutton fat, etc., animal electrometry, mineral oils such as mineral oil, methyl acrylate, butyl acrylate, acrylic I! - Polymers of acrylic esters such as 2-ethyl to lifesil and their oligomers, methacrylic esters such as methyl tutaacrylate, lauryl methacrylate, butyl methacrylate, propyl methacrylate, and -2-ethylhexyl methacrylate, in order of Polymers and their oligomers, styrene, a-
Styrene polymers and their oligomers, vinyl acetate, vinyl butyrate, and other vinyl ester polymers and their oligomers; ethylene, propylene, butanoene, and other unsaturated hydrocarbon polymers; oligomers, copolymers of styrene and acrylic esters and oligomers thereof, copolymers of styrene and 7-tacrylic esters and oligomers thereof,
Ethylene vinyl acetate copolymer, styrene butanoene copolymer, styrene imprene copolymer, acrylonitrile styrene butanoene copolymer, asphalt, petroleum residue such as giltnide, acetylene and butanoene copolymer, Synthetic drying oils such as pentanoene oligomer, carnauba wax, oak berry wax, chanderilla wax, sugar wax, wood wax, vegetable waxes such as skunk, beeswax, white beeswax, spermaceti wax, cef'tsukuku, fluorine, etc. Animals of7@, Montanrou, Osikelite,
Examples include mineral waxes such as hexasilene, and these can be used alone or in combination of two or more. In addition, the following waxes that can be used industrially can also be suitably used. For example, ■ Ester wax (Hoehst Wax E
rKPS, BJ, OPIOM, X22. Un! (10
(synthetic waxes, etc.), ■ Oxidized waxes (waxes obtained by oxidizing waxes such as paraffin wax and microcrystalline wax, Nippon Seiroshaga's NSP)
-9210, N S P-etis, Toyo Vetrofit Company catalog PETR0NABA-C, CARDIS 3
14, Hoechst & Co.*
x S t L r and LP, etc.), ■ Low molecular weight polyethylene wax (especially one with a molecular weight of 3 GG to 1000, manufactured by Toyo Beto Light Co., Ltd. POLIWAX 50)
0 and V655, etc.), and furthermore, microwax (Nisseki Microwax 155.180 (
Nippon Oil Co., Ltd.), HI-M I C-1080% HI-
MIC-2065,) It-MIC-2095, H
l-MIC-1070, HI-MIC-1045, HI
-M I C-2045 (manufactured by Nippon Oil Co., Ltd.), STA
RW A X 10G, B E S Q U
A RE 175°185, V I CTORY, U
Examples include LTRAFLEX (Toyo Betrophyte Shashin Co., Ltd.), stearic acid, behenic acid, stearyl alcohol, dodenyl stearate, stearone, sorbitan monostearate, polyoxyethylene monostearate, and the like. In addition, the core material for heat roll fixing can be any of various heat fixing toner materials, such as styrene, a-
Methylstyrene 59-j-butylstyrene, vinylnaphthalenes, ethylene, propylene, butylene, ibubutylene, vinyl chloride, vinyl acetate, vinyl propionate,
Vinyl butyrate, acrylic acid, methyl, ethyl acrylate,
n-butyl acrylate, acrylic IIF decyl, lauryl acrylate, 2-ethylhexyl acrylate, stearyl heptaacrylate, ethyl tutaacrylate, propyl methacrylate, n-butyl methacrylate, lauryl acrylate, 2-ethylhexyl methacrylate , stearyl methacrylate, acrylonitrile, and ticrylonisilyl, two or more of them may be used in the form of a copolymerization, or they may be further crosslinked using a crosslinking agent. Further, the core material preferably contains a colorant, and for example, in order to obtain a micro-particle toner suitable as a magnetic toner, one of the colorants may be added to the core material. Alternatively, fine powder of magnetic material is contained entirely. As a coloring agent, carbon black, nigrosine dye (
C, 1, No. 504058), 7 Nilinpuru (C,
lNo. 50'405), Calco Oil Blue (C, I, No,
azoie Blue3), Chrome Yellow (C01,
No. 14090), ultramarine blue (C, I,
No, 77103), debon f 4 k? C
, 1, No. 26105), quinoline a-(C
j, No. 47005), methyl chloride (C,f,
No. 52015), 7 taroshi 7 2 puru (C0I, No,
74160), mafkite green off-salate (C1
1, No. 42000), lamp black (C, I, N
o, 77266), a-zuchen (C, 1, No, 4
5435), mixtures thereof, and others, it is necessary that these colorants be contained in a sufficient proportion to form a highly concentrated visible image.゛ The magnetic material may be a metal or alloy showing ferromagnetism such as iron, cobalt, or nickel, including 7-elite or magnetite, or a compound containing these elements, or a material that does not contain a ferromagnetic element but has been subjected to appropriate heat treatment. Alloys that become ferromagnetic when subjected to
Examples include copper-aluminum, manganese-copper-tin and other alloys called Heusler alloys containing manganese and copper, chromium dioxide, and others. Specifically, as magnetite, EPT-1000,
EPT-500, MRM B-450 (and above,
manufactured by Toda Kogyo Co., Ltd.), BL-100, BL-120, BL
-Zoo. BL-220%BL-500, BL-520,
BL-8P. RB-BL, RB-20 (Titan Kogyo Co., Ltd. 91), etc. are preferably used. These magnetic substances are uniformly distributed in the form of fine powder with an average particle size of 0.1 to 1 μm in the core material and/or the outer wall. The content ranges from 920 to 100% by weight per 100 parts by weight of toner.
The weight part is 4G to 7011 parts by weight. When containing fine magnetic powder to make a magnetic toner, it may be treated in the same way as the colorant. As it is, it has low affinity for organic substances such as core materials and monomers, so magnetic fine powder is mixed with so-called coupling agents such as titanium coupling agents, silane coupling agents, surfactants, lecithin, etc. When used after treatment with a ring agent, the magnetic fine powder can be uniformly dispersed.The mixing ratio of each constituent material of the microcapsule type toner of the present invention is preferably the ratio shown in Table 1 below.

【Example】

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. (Example 1) (Example of interfacial polymerization method) Vinyl acetate 1201 as a monomer for core material material, outer wall material! (1), diphenylmethane-4,4'-noisosyphne) 80g1 monomeric polymerization initiator for core material rV
-65J4.8g, magnetic powder B L -520200,
were mixed uniformly and mixed and dispersed for about 1 hour using a sand grinder to obtain a magnetic ink.Next, 20g of coquid tricalcium phosphate, dodecylbene, and 0.2° of sodium insulfonate were added as a dispersion stabilizer. In an aqueous solution containing 300 ml of water, use Homono Efter (**fi Kakogyo Co., Ltd. Il) to adjust the regeneration of the Homono Efter so that the average particle size is 15 μ-, and add it to the water. One fraction of the suspended and dispersed liquid was transferred to a four-necked 7-fusco, and 40 g of xylylennoamine was added dropwise as the outer wall material ([I) into this dispersion, and the mixture was reacted at room temperature for 1 hour.
The temperature was raised to 0°C and the reaction was carried out for 6 hours to polymerize the core material. After this, fluorine alcohol rCF, CF Hz
20 g of OHJ was added dropwise into the dispersion and allowed to react for an additional hour. Then, the dispersion stabilizer was decomposed with hydrochloric acid, filtered and washed with water to remove it, and then dried to obtain the toner of the present invention. This is referred to as "toner 1". (Example 2) A toner of the present invention was obtained by using n-dodenyl tutaacrylate in place of vinyl acetate in Example 1 and using neopentyl glycol in place of xylylenenoamine as the outer wall material ([I). This will be referred to as "toner 2". (Example 3) (Example of in situ polymerization method) Polytutaacrylic acid rhododenle (M n = 35000 - M w / M n = 3.
! 120g Epicoat 819 (Yuka Shell Epoxy Company 1) Bog Ebome) B-001 (Yuka Shell Epoxy Company 1 [) (Epicoat 819 hardening agent)
tog magnetic powder BL-500(
Thank you for the titanium industry! 0 200g lecithin (magnetic powder dispersion and fluidization promoter) 0.6g or more was mixed and mixed uniformly in fractions using sand grain goo to obtain magnetic ink.
Next, as a C1 dispersant, 20 colloidal tricalcium phosphate and 0 sodium dodecylbenzene filtrate
．． Water containing 08g 2! The above magnetic ink was subjected to turbidity separation using Homonoefter (Tokushu Kika Kogyo Co., Ltd. 91) in 1 kg at 1 kg, 000 rpm so that the average particle size was 10 to 15 .mu.m. This suspension liquid a was reacted at 80° C. for 10 hours using a April 1 flask at a stirring speed of 200 rpm to react with Epicote 819 and EVOME) B-001. Microcapsules with an Evokin oil-repellent film formed by applying the resin were obtained. Next, 15" of noaminocyclohexane was added and the reaction was continued for another 5 hours. After the reaction, the dispersion stabilizer was decomposed and removed with hydrochloric acid, filtered,
One toner obtained by washing with water and drying to obtain the toner of the present invention [
"Toner 3". (Example 4) In Example 1, 120 g of styrene was used instead of vinyl acetate.
Furthermore, instead of 80 g of diphenylmethane-4f4'-twin cyanate, polymethylene phenyl isocyanate "Sumitzel 44V-10J (manufactured by Sumitomo Bayer Urethane) 2 was used.
The toner of the present invention was obtained in the same manner except that 1 g and 9 g of "Nipico-) 819J (manufactured by Yuka NEL Eboxy Co., Ltd.) were used. A 0 toner toner of the present invention was designated as "Toner 4." (Example 5) (By coacervate method and spray drying method) Polymethafrylmil ln-dodecyl 4G as core material material
Magnetic powder rB is dissolved in 80 g of methylene chloride.
Add 80 g of L-520J and uniformly mix and disperse in a sand fin. Separately, mix 15 g of urea and 37% formaldehyde aqueous solution @ 40 @, add 10% ethanolamine aqueous solution and adjust 9H to 8. This was kept at 70°C and stirred for about 3 hours to obtain a urea-formaldehyde initial condensate. A homogeneously mixed amount of the drink was suspended and dispersed in a machine with an average particle size of 15 μI by controlling the number of times of the homonoetter. This dispersion was transferred to a four-necked 7-flask, and while stirring, citric acid was gradually added dropwise to adjust the pH to 5. The temperature was maintained at 50°C and stirred for 2 hours (during this time, the core material was Methylene is lI*), and then the pH is adjusted with citric acid.
The temperature was lowered to 3, and the temperature was further kept at 50°C for 5 hours to form an outer wall of the urea-formaldehyde condensate on the droplet surface of the separating liquid. After washing and filtering the capsule particles obtained in this machine, the capsule particles containing 20 parts of excess fat per capsule too! The capsule was mixed with an emulsion of methyl methacrylate/glycitrate methacrylate copolymer and spray-dried using a spray dryer to provide an outer wall of methyl methacrylate/glycitrate methacrylate copolymer on the outside of the capsule. Next, 100 parts of these capsules were dispersed in 300 parts of water containing 0.5% polyvinyl alcohol, and then hexamethylene y amine was added to the mixture.
The reaction was carried out at 0°C for 3 hours. This was filtered and dried to obtain the toner of the present invention. The half toner is referred to as "toner 5". <*m Example 6) Styrene 85゜Butyl acrylate 15g Polyprolene 6g Carbon black 3G (Mitsubishi Carbon Shashin) 10゜7 Zobisparellonitrile 3.5M or more were mixed and divided in a sand grinder at 6 o'clock. The resulting black oil phase was further mixed with 61% colloidal tricalcium phosphate and 0.03% sodium Y-decylbenzenesulfonate. The mixture was mixed with aqueous solution 930064 containing the following, and dispersed at oil temperature using a TK homomixer (manufactured by Tokushu Koki Kogyo Co., Ltd.). For dispersion using the TK homo mixer, the mixer was heated to 9000 r.
p- for 10 minutes and under optical microscope observation 10-1
Oil droplets having an average particle size of about 5 μm were obtained.The oil droplets were placed in a four-bottle flask and allowed to react at 65°C for about 15 hours. After cooling, hydrochloric acid was added to dissolve colloidal tricalcium phosphate, which is a dispersion stabilizer. was decomposed and removed, filtered, washed with water, and dried. Next, 100 parts of the obtained particles were mixed with an emulsion containing 20 parts of a separately prepared methyl/tafrylate/glysitrus tacrylate (O/30) copolymer, and the mixture was spray-dried using a spray dryer. Then, capsules containing the particles as a core material were obtained.
00 parts of polyvinyl alcohol was dispersed in 300 parts of water containing 0.5 wL% of polyvinyl alcohol.
0 part was added and the reaction was carried out at 66°C for 4 hours. After that, the toner of the present invention is obtained by filtering and drying, and the toner is referred to as "Toner 6".
”. (Experimental Example) In the above examples, the amount of charge was measured for the toners before and after treatment with the compound having the armature control curtain. The results are shown in Table 2, where the image side is exclusive amorphous iron powder 5
0g of the toner of the present invention and the toner before treatment 1.51
is added. The amount of triboelectric charge of the toner was measured as follows. The developer sample was triboelectrically charged by exposing it to am for 20 minutes using a [New-Ys shaking racket] (Yashii Inc.).
．． The toner was placed in a metal container with a 350 mesh screen mesh attached to the bottom surface, and nitrogen gas was blown into the container from the upper blowing port at a pressure of 2 kg/cm2 for 3 seconds to screen the toner. 11! Find the amount of charge on J9. The environmental conditions for the measurement are temperature. As shown in Table 2, sufficient triboelectric charging can be obtained by treating the outer wall of the capsule with a compound having a charge control group. Next, using each of the toners in the example of Chiang Kee-kui, the temperature was 50°C and the relative humidity was 8.
Perform an II image evaluation test at a high temperature of 0% and a high temperature of 4. That is, for "toner 1" to "toner 4", electronic copying machine U-B
ix TEN (manufactured by Konishiroku Photo Industry Co., Ltd.), "Toner 5" and "Toner 6" are used for electronic copying. U-Big3
000 (manufactured by Konishiroku Photo Industry Co., Ltd.) photoreceptor modified to match the toner. There was only a slight change in color, and a stable and clear image was obtained. Next, for comparison, in Example 5, a toner was obtained by adding 3 seconds of Pari 7 Hoost dye, which is a negative charge control agent, to the methyl methacrylate/glycyl methacrylate copolymer Emulnon 1, and the image was evaluated in the same manner. Unfortunately, after 10,000 copies, there were more capris, the overall image density decreased, and an image with poor clarity was obtained.

【Effect of the invention】

As is clear from the above description, the toner of the present invention allows extremely suitable Teiden control. Moreover, there is almost no fatigue deterioration even after long-term use.
Effects such as stable image formation are achieved.

Claims (1)

[Claims] A microcapsule type toner comprising a core material containing a fixing component and an outer wall covering the core material, wherein a charge control group is chemically bonded to the outer wall.