JPH0310306B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a toner for developing electrostatic images, and more particularly to a microcapsule type toner that can be suitably used as a pressure fixing type toner. [Prior Art] In recent years, an electrostatic charge image is formed based on image information using electrophotography, electrostatic printing, electrostatic recording, etc., and this is developed with a developer toner to form a toner image. It is widely practiced to form a visible image by transferring this toner image onto a transfer paper or the like and then fixing it. Conventionally, toner for developing electrostatic images has been widely used in powder form, which is obtained by finely pulverizing thermoplastic resin as a binder and colorant such as carbon black dispersed therein. If it is a two-component toner, it is mixed and stirred with a carrier such as iron powder or glass beads, or if it is a one-component toner containing fine magnetic powder, it is stirred itself. , after being triboelectrified and developing an electrostatic charge image using the electrostatic force, and transferring the obtained toner image, for example,
The image is fixed by heating with a heating roller or the like. However, in such toners, the toner particles are crushed during agitation for triboelectric charging, producing fine powder toner, resulting in poor visible image quality or the need to replace the toner with a new one prematurely. In addition, since fixing is achieved by a heat fixing method, a long waiting time is required until the temperature of the fixing device rises to a predetermined set temperature, and a large amount of time is required for heating. In addition, it can cause a fire if a paper jam occurs, and in order to achieve reliable fixing, it is necessary to satisfy fairly strict conditions such as temperature conditions. Under such circumstances, research has recently begun on the use of so-called microcapsules as toners for developing electrostatic images.
This microcapsule type toner is in the form of a powder consisting of colored particles in which a core material made of a liquid substance or a soft solid substance is enclosed in a fine resin capsule (outer wall). When using this toner, fixation can be achieved by applying pressure with a pressure roller or the like to burst the capsule and release the core material inside. Therefore, since no heating is required, there is an advantage that the above-mentioned problems in heat fixing can be significantly alleviated. Regarding such microcapsule type toner that can be fixed under pressure, Japanese Patent Application Laid-Open Nos. 51-91724 and 52-
Techniques described in publications such as No. 119937, No. 54-118249, and No. 55-64251 are known. However, the above technology still has problems such as an offset phenomenon to the pressure roller, durability, stability, and storage stability, and in particular there are problems with pressure fixing properties on plain paper, etc., and microcapsule type toner The fixing component therein was either rigid or excessively plastically deformed, resulting in insufficient fixing properties. Therefore, the inventor of the present invention has conducted intensive studies to improve the pressure fixing properties, and has found that it is insufficient to improve the fixing properties by simply improving the adhesion to paper, etc. It has been found that in order to prevent the film from peeling off from the surface, it is important to reduce the applied external force, that is, to make it slip. Conventionally, as a lubricant-like effect, there is, for example, dimethylsiloxane, which is a mold release agent. This dimethylsiloxane has a great lubricant effect, but on the other hand, it has poor compatibility with resins, etc., so it tends to precipitate when added to toner, and has the disadvantage that it deteriorates the powder characteristics of toner, especially fluidity. . For this reason, when images are formed using microcapsule toner containing dimethylsiloxane (see Japanese Unexamined Patent Publication No. 150968/1983), fogging occurs due to decreased fluidity, and toner There is a problem that the replenishment property becomes poor and the image quality deteriorates.Furthermore, there is a problem that the surface condition of the toner changes easily because it is easily deposited from inside the toner to the outside, and the charging characteristics are unstable. [Object of the Invention] Therefore, an object of the present invention is to provide a pressure-fixable microcapsule type toner having good particle characteristics. Another object of the present invention is to provide a pressure fixable microcapsule type toner having good fixing properties and offset properties. Another object of the present invention is to provide a pressure-fixable microcapsule toner that can provide good images without fogging. Another object of the present invention is to provide a pressure-fixable microcapsule type toner that has good repeatability and durability during continuous use. Another object of the present invention is to provide a pressure-fixable microcapsule type toner that is easy to manufacture, can be produced stably, and has a low manufacturing cost. Another object of the present invention is to provide an excellent, marketable, pressure-fixable microcapsule toner that satisfies various properties required of a pressure-fixable microcapsule toner in a well-balanced manner. [Structure of the Invention] As a result of extensive research, the present inventor has found that in a pressure-fixable microcapsule toner consisting of an outer wall and a core material, at least the core material contains silicone oil represented by the following general formula. It has been found that the above object can be achieved by a pressure fixable microcapsule type toner characterized by the following. [In the formula, R represents an alkyl group or an alkenyl group having 4 to 15 carbon atoms. In the formula, m and n are integers,
+n=5-200. ] The silicone oil of the present invention is substantially liquid at room temperature. Therefore, it has a higher mold release effect (lubricant effect) than a solid one, and since it is liquid, it has high compatibility, so it has a high plasticizing effect in the core material, so it has good "spreading" during fixing and is effective. The fixing area also becomes larger, and as a result, the fixing performance can be improved, and it is thought that the above object can be achieved by this. Preferred silicone oils of the present invention include compounds represented by the following general formula. In the above formula, m and n are integers, +=5 to 200,
m:n=1:9 to 9:1, and R is the number of carbon atoms to
15, preferably 4 to 15 alkyl or alkenyl groups. The silicone oil of the present invention has a viscosity of 1×10 ⁵ cst
(At 25°C) The following is a preferable range in which the liquid exhibits a substantially liquid state. (Exemplary Compound) Specific exemplary compounds of the silicone oil of the present invention can be obtained by substituting and combining the following conditions, the values of m and n determined in the range of +=5 to 200, and the terminal group described below into the above formula. It is something that can be done. (i) R=C ₅ H ₁₁ m:n=3:7 (ii) R=C ₅ H ₁₁ m:n=5:5 (iii) R=C ₅ H ₁₁ m:n=7:3 (iv ) R=C ₁₀ H ₂₁ m:n=3:7 (v) R=C ₁₀ H ₂₁ m:n=5:5 (vi) R=C ₁₀ H ₂₁ m:n=7:3 (vii) R =C ₁₅ H ₃₁ m:n=3:7 (viii) R=C ₁₅ H ₃₁ m:n=5:5 (ix) R=C ₁₅ H ₃₁ m:n=7:3 (x) R=C ₁₀ H ₁₉ m:n=5:5 () R=C ₁₀ H ₁₉ m:n=7:3 () R=C ₁₅ H ₂₉ m:n=5:5 () R=C ₁₅ H ₂₉ m: n=3:7 The silicone oil of the present invention can also be obtained from commercial products, such as SH-203, SH-230, SF-
8416 (manufactured by Toray Silicon), X-22-711,
Examples include KF-412, KF-413, and KF-414 (manufactured by Shin-Etsu Chemical Co., Ltd.). The terminal group of the silicone oil of the present invention is not particularly limited, but generally preferably has the following structure. In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, an alkenyl group, an allyl group, an aralkyl group, etc. The silicone oil of the present invention is contained in the core material, and if necessary, in the core material and outer wall, and the amount added is determined in the microcapsule type toner.
It ranges from 0.5 to 10 wt%, preferably from 1.0 to 5.0 wt%. The method for manufacturing the microcapsule toner of the present invention can utilize various known encapsulation techniques. For example, spray drying method, interfacial polymerization method (a method in which components in the suspended and dispersed particles polymerize and react with components in the dispersion medium at the interface of the particles to form a resin film), coacelvation method, in-situ polymerization method,
Phase separation method, U.S. Patent No. 3338991,
The methods described in the specifications of No. 3326848 and No. 3502582 can be used. Among them, interfacial polymerization method can be effectively used. This is because it is easy to form the outer wall and it is easy to separate the functions of the core material and wall material. Furthermore, the outer wall material constituting the microcapsule type toner is not particularly limited, but epoxy resins, polyamide resins, polyurethane resins, polyurea resins, vinyl resins, and other resins are preferably used for practical purposes and are stable in storage. Polyurethane resin, in terms of properties and quick reaction time in production,
Particular preference is given to using polyurea resins. Epoxy resin is a resin produced by a reaction between an epoxy resin or a compound containing an epoxy group and a curing agent. Examples of these epoxy resins or compounds containing epoxy groups include the following, but are not particularly limited as long as they have two or more epoxy groups in the molecule.

【table】

【table】

[Table] The above curing agents include ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, other aliphatic polymine compounds, xylylenediamine,
Other aromatic polyamine compounds are typical, and commercially available products include Epiquure T, Epiquure U, Epiquure 103, Epomate B-001, Epomate LX-IN, and Epomate PX-3 (all of which are manufactured by Yuka Ciel Epoxy Co., Ltd.). Other commonly known epoxy curing agents include epoxy curing agents such as epoxy curing agents such as Examples of polyamide resins include so-called polyamide resins obtained by the reaction of carboxylic acid chlorides such as sebacyl chloride, terephthalic acid chloride, and adipic acid chloride with aliphatic polyamines and aromatic polyamines exemplified as curing agents for the above-mentioned epoxy resins. Polyamide resin can be used. Polyurethane resins are obtained by reacting polyisocyanates with polyols, and polyurea resins are obtained by reacting polyisocyanates with polyamines. Specific examples of polyisocyanates include the following.

【table】

【table】

【table】

[Table] Specific examples of polyols or polyamines that react with the above polyisocyanates to produce polyurethane resins or polyurea resins include the following. 1 Polyol ethylene glycol, propylene glycol,
Diols such as butylene glycol and hexamethylene glycol, triols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, water, and others. 2 Polyamine ethylene diamine, hexamethylene diamine,
Diethylenetriamine, iminobispropylamine, phenylenediamine, xylenediamine, triethylenetetramine, and others. Furthermore, vinyl polymerizable monomers for obtaining vinyl resins include styrenes such as styrene, parachlorostyrene, α-methylstyrene, and t-butylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, α-methylene aliphatic monocarboxylic acid esters such as stearyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate; Vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl methyl ether,
Vinyl ethers such as vinyl isobutyl ether, vinyl pyridines such as 2-vinylpyridine and 4-vinylpyridine, N-vinyl cyclic compounds such as N-vinylpyrrolidone, vinyl methyl ketone, vinyl ethyl ketone, methyl isopropenyl ketone, etc. Vinyl ketones, unsaturated hydrocarbons such as ethylene, propylene, isobutylene, butadiene, and isoprene, halogen-containing unsaturated hydrocarbons such as chloroprene, and other monofunctional vinyl monomers can be used alone or in combination. In addition to the above monofunctional monomers, polyfunctional vinyl monomers can also be used, and these polyfunctional monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol. Polyhydric alcohol methacrylates such as dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol tetramethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neo Polyhydric alcohol acrylates such as pentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritol tetraacrylate, polyfunctional vinylbenzenes such as divinylbenzene, and others can be used alone or in combination. Furthermore, these polyfunctional monomers may be used in combination with the monofunctional monomers described above. The core material constituting the microcapsule type toner of the present invention contains a pressure fixing substance, and the substances include liquid polybutene, liquid polyfluoroprene, adipic acid polyester, liquid polyester, dibutyl phthalate, dioctyl phthalate, chlorinated Plasticizers such as paraffin, linoleic acid, linolenic acid, oleic acid, elaidic acid, eleostearic acid, linolenic acid, gadolenic acid, erucic acid, arachidonic acid, culpanodonic acid, α-
Esters of unsaturated fatty acids such as lycanic acid, linseed oil, eno oil, tung oil, castor oil, hemp seed oil, kapotsk oil, poppy seed oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil Vegetable oils such as oil, sunflower oil, cottonseed oil, olive oil, animal oils such as squid oil, sardine oil, saury oil, whale oil, beef tallow, lard, mutton tallow, mineral oils such as mineral oil, methyl acrylate, butyl acrylate , polymers of acrylic esters such as 2-ethylhexyl acrylate and oligomers thereof, methyl methacrylate, lauryl methacrylate, butyl methacrylate, propyl methacrylate, methacrylate
Polymers of methacrylic acid esters such as 2-ethylhexyl and their oligomers, styrene, α
- Polymers of styrenes such as methylstyrene and oligomers thereof, polymers of vinyl esters such as vinyl acetate and vinyl butyrate and oligomers thereof, polymers of unsaturated hydrocarbons such as ethylene, propylene, butadiene, etc. oligomers,
Copolymers of styrene and acrylic esters and oligomers thereof, copolymers of styrene and methacrylic esters and oligomers thereof, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers ,
acrylonitrile styrene butadiene copolymer,
Petroleum residues such as asphalt and gilsonide, synthetic drying oils such as copolymers of acetylene and butadiene, and dicyclopentadiene oligomers, vegetable waxes such as carnauba wax, oak lily wax, chandelilla wax, sugar wax, wood wax, and scarlet, beeswax, and salami. Beeswax, spermaceti wax, serrata wax,
Examples include animal waxes such as lanolin, and mineral waxes such as montan wax, ozokerite, and ceresin, and these may be used alone or in combination of two or more. The following waxes that can be produced industrially can also be suitably used. For example, ester wax (Hoechst Wax E, F, KP,
Synthetic ester waxes such as KPS, BJ, OP, OM, NPS-9210, NPS-6115, PETRONABA・C manufactured by Toyo Petrolite Co., Ltd., CARDIS314
, Hoechst Wax S, L, and
LP, etc.), low molecular weight polyethylene waxes (particularly those with a molecular weight of 300 to 1000, such as POLYWAX 500 and 655 manufactured by Toyo Petrolite Co., Ltd.), and micro waxes (Nisseki Micro Wax 155, 180, etc.). (manufactured by Nippon Oil Co., Ltd.), HI−MIC−
1080, HI-MIC-2065, HI-MIC-2095, HI-
MIC−1070, HI−MIC−1045, HI−MIC−2045
(manufactured by Nippon Seirosha), STAR WAX 100, BE
SQUARE 175, 185, VICTORY, ULTRA
FLEX (manufactured by Toyo Petrolite Co., Ltd.), stearic acid, behenic acid, stearyl alcohol, dodecyl stearate, stearone, sorbitan monostearate, polyoxyethylene monostearate, and the like. Further, the content of the pressure fixing substance contained in the core material in the toner is 5 to 45 wt%, preferably
It is 15-35wt%. In addition, the core material preferably contains a colorant, but in order to obtain a microcapsule toner suitable as a magnetic toner used as a one-component toner, for example, magnetic toner may be included as part or all of the colorant. Contains fine body powder. Coloring agents include carbon black, nigrosine dye (CI No. 50415B), and aniline blue (CI No.
50405), Calco Oil Blue (CINo.azoic
Blue3), Chrome Yellow (CINo.14090), Ultramarine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CI
No. 47005), methylene blue chloride (CI No.
52015), Phthalocyanine Blue (CINo.74160),
Malachite Green Oxalate (CINo.
42000), lampblack (CI No. 77266), rose bengal (CI No. 45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a high-density visible image, and are usually contained in a proportion of about 0 to 20 parts by weight per 100 parts by weight of the pressure fixable material. It will be done. The magnetic material may be a metal or alloy showing ferromagnetism such as ferrite, magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. alloys that exhibit ferromagnetic properties due to the presence of metals, such as alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others. . Specifically, as magnetite, EPT−
1000, EPT-500, MRMB-450 (manufactured by Toda Kogyo Co., Ltd.), BL-100, BL-120, BL-200, BL-
220, BL-500, BL-520, BL-SP, RB-BL,
RB-20 (manufactured by Titanium Kogyo Co., Ltd.) and the like are preferably used. These magnetic substances are uniformly dispersed in the pressure fixable material in the form of fine powder with an average particle size of 0.1 to 1 μm.
The content is 20 to 100 parts by weight of toner.
70 parts by weight, preferably 40 to 70 parts by weight. In addition, when containing magnetic fine powder to make a magnetic toner, it can be treated in the same way as the colorant, but if it is left as it is, the affinity for organic substances such as core materials and monomers will be reduced. Therefore, if the magnetic fine powder is used together with a so-called coupling agent such as a titanium coupling agent, a silane coupling agent, or lecithin, or after being treated with a coupling 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 as shown in the table below.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 (Example of in situ polymerization method) Liquid polyptene 128g Exemplary compound () (commercial product name: (manufactured by Titan Kogyo Co., Ltd.) 200g The above substances were mixed and uniformly mixed and dispersed for about 30 minutes using a sand grinder to obtain a magnetic ink. Next, in 2000 ml of water containing 20 g of colloidal tricalcium phosphate and 0.08 g of sodium dodecylbenzene sulfonate as a dispersion stabilizer, it was mixed at a rotation speed of 7,000 to 8,000 rpm using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.). The above magnetic ink was suspended and dispersed so that the average particle size was 15 μm. This suspended dispersion was transferred to a four-necked flask and reacted at 75° C. for 8 hours at a stirring speed of 200 rpm. After the reaction, the dispersion stabilizer was decomposed and removed with hydrochloric acid, filtered, washed with water, and dried to obtain the toner of the present invention. This toner will be referred to as "Toner 1". Example 2 (Example of in situ polymerization method) Polyvinyl acetate (Mw=35000, Mw/Mn=
3.5) 118g Exemplary compound () (Commercial product name: X-22-711)
12g Epicote 819 (manufactured by Yuka Ciel Epoxy Co., Ltd.) 60 g Epomate B-001 (manufactured by Yuka Ciel Epoxy Co., Ltd.)
(Epicote 819 hardening agent) 10g Magnetic powder BL-500 (manufactured by Titanium Industries) 200g Lecithin (magnetic powder dispersion and fluidization promoter)
Mix 0.6g or more and use a sand grinder to uniformly disperse and mix to obtain magnetic ink. Then, colloidal tricalcium phosphate was used as a dispersion stabilizer.
20g and sodium dodecylbenzenesulfonate
The above magnetic ink was suspended and dispersed in water 2 containing 0.08 g at a rotation speed of 9000 rpm using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.) so that the average particle size was 10 to 15 μm. This suspension dispersion was stirred at 80℃ using a four-necked flask at a stirring speed of 200rpm.
After reacting for 10 hours, Epicote 819 and Epomate B-
001 to form microcapsules with an epoxy resin film. After the reaction, the dispersion stabilizer was decomposed and removed with hydrochloric acid, filtered, washed with water, and dried to obtain the toner of the present invention. This toner will be referred to as "toner 2." Example 3 (Example of interfacial polymerization method) As a core material material, 108 g of ethylene-vinyl acetate copolymer, exemplified compound (i) (viscosity 150cst, 25°C) 12
Add 100 ml of methylene chloride to g to make a uniformly molten solution. Next, 80 g of polymethylene phenyl isocyanate "Millionate MR" (manufactured by Nippon Polyurethane Industries Co., Ltd.) was added as an outer wall material (), and the mixture was homogeneously dissolved in a sand grinder.
Add 200g of magnetic powder BL-120 (manufactured by Titan Kogyo Co., Ltd.),
The mixture was mixed and dispersed uniformly for about 1 hour using a sand grinder to obtain a magnetic ink. Next, using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.), the above homogeneous mixed dispersion was dispersed into an aqueous solution 3 containing 20 g of colloidal tricalcium phosphate and 0.2 g of sodium dodecylbenzenesulfonate as a dispersion stabilizer. The homogeator rotation speed was adjusted so that the diameter was 15 μm, and the particles were suspended and dispersed in water. Transfer the suspension dispersion to a four-necked flask, maintain the liquid temperature at 35°C to 40°C,
Distill and remove methylene chloride. Then xylylene diamine is added as the outer wall material () into this dispersion.
20 g was added dropwise and the dispersion was stirred for about 3 hours to cause "Millionate MR" and xylylene diamine to react at the interface of the dispersion droplets, forming an outer wall of polyurea on the surface of the dispersion droplets. After the reaction, the dispersion stabilizer was decomposed and removed with hydrochloric acid, washed with filtration and water, and then dried to obtain the toner of the present invention. This toner will be referred to as "Toner 3." Example 4 (Example of interfacial polymerization method) As the monomer for the core material, vinyl acetate 108, exemplified compound (vii) (viscosity 215cst, 25°C) 12g, as the outer wall material (), diphenylmethane-4,4'- Uniformly mix diisocyanate 80, 4.3 g of monomeric polymerization initiator for core material "V-65", and 200 g of magnetic powder BL-520, and use a sand grinder to mix and disperse for about 1 hour to obtain magnetic ink. . Next, using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.), the above homogeneous mixed dispersion was dispersed into an aqueous solution 3 containing 20 g of colloidal tricalcium phosphate and 0.2 g of sodium dodecylbenzenesulfonate as a dispersion stabilizer. The homogeator rotation speed was adjusted so that the diameter was 15 μm, and the particles were suspended and dispersed in water. Transfer the dispersion liquid to a four-necked flask, drop 40 g of xylylene diamine as an outer wall material () into this dispersion liquid,
React for 1 hour at room temperature. Then, the temperature was raised to 60°C and reacted for 6 hours to polymerize the core material. After this, the dispersion stabilizer is decomposed and removed with hydrochloric acid, and
After washing with water and drying, a toner of the present invention was obtained.
This toner will be referred to as "Toner 4". Example 5 (Example of interfacial polymerization method) In Example 4, diphenylmethane-4,
Instead of 80 g of 4'-diisocyanate, 56 g of diphenylmethane-4,4'-diisocyanate,
Using 24 g of "Epicote 819", the reaction was carried out at 60°C for 6 hours and then at 80°C for 10 hours to obtain the toner of the present invention. This toner will be referred to as "Toner 5." Example 6 (Example using coacervate method and spray drying method) Magnetic powder "BL-
520'' was added and uniformly mixed and dispersed using a sand grinder. Separately, mix 15 g of urea and 40 g of 37% formaldehyde aqueous solution, add 10% ethanolamine aqueous solution, adjust the pH to 8, and mix this.
The mixture was kept at 70°C and stirred for about 3 hours to obtain a urea formaldehyde initial condensate. Then, this initial condensate
The above homogeneous mixed dispersion was added to 250 ml of an aqueous solution containing 30 g using a homogeator, and the average particle size was 15 μm.
Adjust the rotation speed of the homogenizer so that
It was suspended and dispersed. This dispersion was transferred to a four-necked flask, and while stirring, enoic acid was gradually added dropwise to adjust the pH.
5, keep the temperature at 50°C, and stir for 2 hours (during this time, the methylene chloride in which the core material was dissolved will evaporate). Furthermore, lower the pH to 3 with citric acid,
The mixture was further maintained at 50° C. for 5 hours to form an outer wall of the urea-formaldehyde condensate on the surface of the dispersed droplets. After washing and filtering the capsule particles thus obtained, they are mixed with a separately prepared emulsion of styrene-acrylic copolymer containing 20 parts of resin per 100 parts of capsules, and then sprayed with a spray dryer. After drying, add styrene to the outside of the capsule.
An outer wall of acrylic copolymer was provided. In this way, the toner of the present invention was obtained. This toner will be referred to as "Toner 6". Example 7 A toner of the present invention was obtained in the same manner as in Example 5, except that 3 g of Exemplified Compound () (viscosity 505 cst, 25° C.) was used instead of Exemplified Compound (vii). This is called "Toner 7". Example 8 A toner of the present invention was produced in the same manner as in Example 5, except that 20 g of exemplified compound (v) (commercial product name: "X-22-711" manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of exemplified compound (vii). I got it. This will be referred to as "toner 8". Example 9 In Example 2, magnetic powder "BL-500", 200g
A toner of the present invention was obtained in the same manner except that 100 g of "BL-500" was used instead of "BL-500". This is "Toner 9"
shall be. Example 10 In Example 3, 200g of magnetic powder “BL-120”
A toner of the present invention was obtained in the same manner except that 100 g of "BL-520" was used instead. This is "Toner 10"
shall be. Example 11 In Example 5, 200g of magnetic powder “BL-520”
A toner of the present invention was obtained in the same manner except that 100 g of "BL-520" was used instead. This is called "toner"
11". Example 12 In the same manner as in Example 6 except that 20 g of “BL-120” was used instead of 40 g of “BL-520”,
A toner of the present invention was obtained. This toner is referred to as "Toner 12." Example 13 In Example 5, 10 g of exemplified compound (vii),
A toner of the present invention was obtained in the same manner except that 15 g of carbon black (Mitsubishi Carbon Black #30, manufactured by Mitsubishi Chemical Industries, Ltd.) was used instead of 200 g of the magnetic powder "BL-520." This toner will be referred to as "Toner 13." Example 14 In Example 6, the exemplified compound () was reduced to 1.5
carbon black (Monarch880, manufactured by Cabot) instead of 40g of magnetic powder "BL-520"
A toner of the present invention was obtained in the same manner except that 1 g was used. This toner is referred to as "Toner 14." Comparative Example 1 A toner was obtained in the same manner as in Example 5 except that exemplified compound (vii) was omitted. This toner is referred to as "comparison toner 1." Comparative Example 2 A toner was obtained in the same manner as in Example 13 except that exemplified compound (vii) was omitted. This toner is referred to as "comparison toner 2." Comparative Example 3 A toner was obtained in the same manner as in Example 5, except that polydimethylsiloxane SH-200 (10,000 cst, manufactured by Toray Silicone Co., Ltd.) was used as the exemplified compound (vii). This toner will be referred to as "Comparison Toner 3." Comparative Example 4 Magnetic powder “BL” was added to 100 g of ethylene-vinyl acetate copolymer.
100 g of "-520" was added, kneaded, mixed and crushed to obtain a toner. This toner will be referred to as "Comparison Toner 4." Comparative Example 5 In Example 5, R instead of exemplified compound (vii)
A toner was obtained in the same manner except that a compound of =C ₃₀ H ₆₁ (X-22-713, manufactured by Shin-Etsu Chemical Co., Ltd., mp = about 60°C) was used. This toner will be referred to as "Comparison Toner 5." Comparative Example 6 A toner was obtained in the same manner as in Example 5, except that polydimethylsiloxane KF-96 (300 cst; manufactured by Shin-Etsu Silicone) was used as the exemplary compound (). The results of evaluating this toner are shown in the table. In addition, in the fixability evaluation, similar to Comparative Example 3, an abnormality occurred in the image, so evaluation was impossible. Experimental Example 1 Electrophotographic performance was evaluated using toners "Toner 1" to "Toner 14" of the present invention. Evaluation of powder properties is shown in Table-1. As powder characteristics evaluation, the fluidity of the powder was evaluated based on the static bulk density, and the triboelectric charging property was evaluated by measuring the amount of charge using the blow-off method. Static bulk density is 0.4 with silica powder in toner.
% (weight) and mixed uniformly using a V-type mixer, and then measured using a tapdenser KYT-2000 (manufactured by Seishin Enterprise Co., Ltd.). The amount of charge was determined by mixing 2g of the sample with a conductive iron powder carrier (toner concentration: 3%) as a developer and shaking it for a predetermined period of time using a "New-Ys shaker" (manufactured by Yayoi Co., Ltd.) to triboelectrically charge the sample. Place a 350-mesh screen mesh in a metal container and blow nitrogen gas at a pressure of 0.2 kg/cm ² for 3 seconds through the nozzle to scatter the toner from the screen mesh to remove the remaining carrier charge. was measured by the blow-off method using a voltmeter. The environmental conditions for measurement were a temperature of 20°C and a relative humidity of 60%.

[Table] Thus, it can be seen that the toner of the present invention has better powder characteristics than Comparative Toner 3. Next, using the toner of the present invention and the comparative toner,
Developing and fixing were performed, and fixing properties and offset properties were evaluated. "Toner 1" to "Toner 8" and "Comparison Toner 1", "Comparison Toner 3" to "Comparison Toner 5"
was evaluated using a U-Bix TEN (manufactured by Konishiroku Photo Industry Co., Ltd.) fixing machine modified into a pressure fixing machine (20 kg/cm). Also “Toner 9”~
For "Toner 12", NP-122 (manufactured by Canon)
machines were evaluated. Furthermore, "Toner 13", "Toner 14", and "Comparative Toner 2" are mixed with a conductive iron powder carrier (average particle size: 100 μm) to form a developer with a toner concentration of 3%. Next, an evaluation was performed using a U-Bix V ₃ R (manufactured by Konishiroku Photo Industries Co., Ltd.) machine in which the photoreceptor was replaced with an organic semiconductor and the fixing device was replaced with a pressure fixing device. With the toner of the present invention, a clear image without fogging was obtained, but with Comparative Toner 3, the fluidity was low, so the image quality deteriorated, there was a lot of fogging, and the image was uneven. This is because Comparative Toner 3 uses incompatible dimethylsiloxane.
This is thought to be due to the precipitation of siloxasane on the surface of the particles, which deteriorated the surface properties of the powder. The fixability was evaluated as follows. Using the solid black part (reflection density = 1.0), dyeing friction resistance tester A-3010 (manufactured by Daiei Scientific Precision Manufacturing Co., Ltd.)
Adjust the load to 2 kg using
By Bix Paper55Kg grade (manufactured by Konishiroku Photo Industry Co., Ltd.)
It was rubbed 10 times and the change in reflection density was evaluated as a percentage. Offset property was evaluated by measuring the amount of the solid black area adhered to the fixing roller after copying 10 sheets of 20 cm square solid black area. These results are shown in Table-2.

[Table] As described above, it can be seen that the toner of the present invention has good fixing properties.

Claims (1)

[Scope of Claims] 1. A pressure fixable microcapsule type toner comprising an outer wall and a core material, wherein at least the core material contains silicone oil represented by the following general formula. mold toner. [In the formula, R represents an alkyl group or an alkenyl group having 4 to 15 carbon atoms. In the formula, m and n are integers,
+n=5-200. ]