JPH0310308B2 - - 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 by electrophotography, electrostatic printing, electrostatic recording, etc., and this is developed with toner of a developer 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 by itself. After the toner image is triboelectrified and the electrostatic force is used to develop the electrostatic charge image, and the resulting toner image is transferred, 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 new ones prematurely. Not only is this necessary, but since fusing is achieved by a heat fusing method, a long waiting time is required until the temperature of the fusing device rises to the required set temperature, and It requires a large amount of energy and can even cause a fire if a paper jam occurs. Moreover, 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 offset development on the pressure roller, durability, stability, and storage stability.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 a toner, and has the disadvantage that the powder properties of the toner, especially its fluidity, deteriorate. . For this reason, when images are formed using microcapsule toner containing dimethylsiloxane (see Japanese Patent Application Laid-open 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 toner having good particle properties. 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. [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 a carboxylic acid-modified 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 containing: [In the formula, x and y are integers, +=2 to 200
It is. R' represents an alkylene group having 2 to 40 carbon atoms. ] The carboxylic acid-modified silicone compound of the present invention has high compatibility with toner resin due to its polar effect, so it has good powder properties, especially good fluidity,
In addition, since it has an excellent effect as a lubricant, it is thought that both of these effects can be used together to achieve the above objective. The terminal group of the carboxylic acid-modified 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. Examples of the carboxylic acid-modified silicone oil of the present invention include SF-8418 (manufactured by Toray Silicone Co., Ltd.),
-22-3701E, X-22-3710, X-22-3715,
Commercial products such as KF-910, X-22-800, and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. It is contained in the core material, and if necessary, in the core material and outer wall, and the amount added is 0.5 to 10 wt%, preferably 1.0% in the microcapsule type toner.
It is in the range of ~5.0wt%. 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】

[Table] Furthermore, as an example of a commercially available product, “Epicote
807,""Epicoat827,""Epicoat190,""EpicoatYX-310," and "Epicoat DX-255" (manufactured by Yuka Ciel Epoxy Co., Ltd.). The above-mentioned curing agents include ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, other aliphatic polyamine compounds, xylylenediamine, phenylenediamine, and other aromatic polyamines. Typical compounds include Epiquure T, Epiquure U, and Epiquure U.
103, Epomate B-001, Epomate LX-IN,
Epomate PX-3 (manufactured by Yuka Ciel Epoxy Co., Ltd.) and other commonly known epoxy curing agents can be used. 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, glycerin, triols such as trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, and water, Others 2 Polyamine Ethylenediamine, hexamethylenediamine,
Diethylenetriamine, iminobispropylamine, phenylenediamine, xylenediamine, triethylenetetramine, etc. Vinyl polymerizable monomers for obtaining vinyl resin include styrene, parachlorostyrene, α-methylstyrene, t-butylstyrene. Styrenes such as methyl acrylate, ethyl acrylate, n-propyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-methacrylate -α-methylene aliphatic monocarboxylic acid esters such as ethylhexyl 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 examples of the substance include liquid polybutene, liquid polychloroprene,
Adipic acid polyester, liquid polyester,
Plasticizers such as dibutyl phthalate, dioctyl phthalate, chlorinated paraffin, linoleic acid, linolenic acid, oleic acid, elaidic acid, eleostearic acid, linolenic elaidic 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, Vegetable oils such as rapeseed oil, sunflower oil, cottonseed oil, olive oil, squid oil, sardine oil, saury oil, whale oil, beef tallow, pork fat,
Animal oils such as mutton fat, mineral oils such as mineral oil,
Polymers of acrylic esters such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and oligomers thereof, methyl methacrylate, lauryl methacrylate, butyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, etc. Polymers of methacrylic acid esters 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, styrene-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
and Hoechst Wax S, L and LP manufactured by Hoechst.
etc.), low molecular weight polyethylene wax (especially those with a molecular weight of 300 to 1000, manufactured by Toyo Petrolite)
POLYWAX 500 and 655, etc.), and microwaxes (Nisseki Microwax 155, 180 (manufactured by Nippon Oil Corporation), HI-MIC-
1080, HI-MIC-2065, HI-MIC-2095, HI-
MIC-1070, HI-MIC-1045, HI-MIC-2045
(manufactured by Nippon Seirosha), STAR WAX100, BE
SQUARE175, 185, VICTORY,
ULTRAFLEX (manufactured by Toyo Petrolite Co., Ltd.), stearic acid, behenic acid, stearyl alcohol,
Examples include dodecyl stearate, stearon, 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 chloride (CINo.52015),
Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo.42000), Lampblack (CINo.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 0 parts by weight per 100 parts by weight of the pressure fixable material.
The proportion is approximately 20 parts by weight. The magnetic material may be a ferromagnetic metal or alloy such as iron, cobalt, or nickel, including ferrite and magnetite, 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 become ferromagnetic, such as manganese-copper-aluminum,
Mention may be made of a type of alloy called Heusler alloy containing manganese and copper, such as 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 fixing 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 polybutene 128g (manufactured by Titan Kogyo Co., Ltd.) 200g] Mix the above substances, use a sand glider,
The mixture was uniformly mixed and dispersed for about 30 minutes to obtain a magnetic ink.
Next, in 2000 ml of water containing 20 g of colloidal tricalcium phosphate and 0.08 g of sodium dodecylbenzenesulfonate as a dispersion stabilizer, the rotation speed was adjusted using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.).
The above magnetic ink was suspended and dispersed under conditions of 7000 to 8000 rpm 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 KF-910 (mp45℃, manufactured by Shin-Etsu Chemical Co., Ltd.) 12g Epicote 819 (manufactured by Yuka Ciel Epoxy Co., Ltd.) 60g 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)
0.6g] Mix the above ingredients 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 with an average particle size of 10 to 15 μm was added to water 2 containing 0.08 g at a rotation speed of 900 rpm using a homogeator (manufactured by Tokushu Kika Kogyo Co., Ltd.).
It was suspended and dispersed so that Using a four-necked flask, stir this suspension dispersion at a stirring speed of 200 rpm to 80%
℃ for 10 hours to form microcapsules having an epoxy resin film formed by reacting Epicote 819 with Epomate B-001. After the reaction, the dispersion stabilizer is decomposed and removed with hydrochloric acid, and
The toner of the present invention was obtained by washing with water and drying. This toner will be referred to as "toner 2." Example 3 (Example of interfacial polymerization method) As a core material, 108 g of ethylene-vinyl acetate copolymer and 12 g of X-22-3715 (25°C, viscosity 200 cst, manufactured by Shin-Etsu Chemical Co., Ltd.) were added with 100 ml of methylene chloride.
Make a uniformly dissolved solution. Next, 80 g of polymethylene phenyl isocyanate "Millionate MR" (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was added as an outer wall material () and the mixture was made into a homogeneous solution using a sand grinder, followed by 200 g of magnetic powder BL-120 (manufactured by Titan Kogyo Co., Ltd.). was mixed and dispersed uniformly for about 1 hour using a sand grinder 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 rotation speed of the homogenizer was adjusted so that the diameter was 15 μm, and the particles were suspended and dispersed in water. The suspension dispersion is transferred to a four-necked flask, the temperature of the liquid is maintained at 35°C to 40°C, and methylene chloride is distilled off. Then add the outer wall material () into this dispersion
20 g of xylylene diamine 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 material, 108 g of lauryl methacrylate, 12 g of X-22-800 (mp64°C, manufactured by Shin-Etsu Chemical Co., Ltd.), as the outer wall material (2), diphenylmethane-4, 80 g of 4'-diisocyanate, 4.3 g of monomeric polymerization initiator "V-65" for core materials, and 200 g of magnetic powder BL-520 (manufactured by Titan Kogyo Co., Ltd.) were mixed uniformly, and mixed using a sand grinder for about 1 hour. mixture·
Disperse 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 rotation speed of the homogenizer 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. Next, the temperature is raised to 60°C and the reaction is carried out for 6 hours to polymerize the core material.
After that, the dispersion stabilizer was decomposed and removed with hydrochloric acid.
After filtering and washing with water, it was dried to obtain a toner of the present invention. 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) As the core material material, X-22-3701E (25°C, viscosity
3000cst, manufactured by Shin-Etsu Chemical Co., Ltd.) 3g, polyvinyl acetate 20g dissolved in 40g of methylene chloride,
40 g of magnetic powder "BL-520" was added and mixed and dispersed uniformly using a sand grinder. Separately urea 15
g and 40 g of 37% formaldehyde aqueous solution,
A 10% aqueous ethanolamine solution was added to adjust the pH to 8, and the mixture was kept at 70°C and stirred for about 3 hours to obtain a urea formaldehyde initial condensate. Then,
The homogeneous mixed dispersion was suspended and dispersed in 250 ml of an aqueous solution containing 30 g of this initial condensate by adjusting the rotational speed of the homogeter so that the average particle size was 15 μm. Transfer this dispersion to a four-necked flask, and while stirring, gradually add citric acid dropwise to bring the pH to 5. Keep the temperature at 50°C and stir for 2 hours (during which time the core material was dissolved). methylene chloride evaporates). Further, the pH was lowered to 3 with citric acid, and the mixture was further kept 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, an outer wall of styrene-acrylic copolymer was provided on the outside of the capsule. In this way, the toner of the present invention was obtained.
This toner will be referred to as "Toner 6". Example 7 In Example 5, instead of X-22-800,
A toner of the present invention was obtained in the same manner except that 3 g of X-22-3710 (25° C., viscosity 50 cst) was used. This is called "Toner 7". Example 8 In Example 5, instead of X-22-800,
A toner of the present invention was obtained in the same manner except that 20 g of X-22-3715 (25° C., viscosity 200 cst) was used. This will be referred to as "toner 8". Example 9 In Example 2, 200g of magnetic powder “BL-500”
A toner of the present invention was obtained in the same manner except that 100 g of "BL-500" was used instead. This will be referred to as "toner 9." 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 called "toner"
10". 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, instead of X-22-800,
Carbon black (Mitsubishi Carbon Black #30, Mitsubishi Chemical Industries) 15
A toner of the present invention was obtained in the same manner except that g was used. This toner will be referred to as "Toner 13." Example 14 In Example 6, instead of X-22-3701E, 1.5 g of X-22-3710 (25°C, viscosity 50 cst), and 40 g of magnetic powder "BL-520", carbon black (Monarch 880 manufactured by Cabot Co., Ltd.) were used. A toner of the present invention was obtained in the same manner except that 1 g of the product 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 X-22-800 was removed. 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 X-22-3715 was removed. 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 cs. manufactured by Toray Silicone Co., Ltd.) was used instead of X-22-800. 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 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 instead of X-22-800. The results of evaluating this toner are shown in the table. In addition, in the fixability evaluation, as in Comparative Example 3, an abnormality occurred in the image, so evaluation was impossible. Experimental Example 1 Using the toners "Toner 1" to "Toner 14" of the present invention, electrophotographic performance was evaluated. Evaluation of powder properties is shown in Table-1. To evaluate the powder properties, 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. The static bulk density was measured by adding 0.4% (by weight) of silica powder to the toner, mixing the mixture uniformly using a V-type mixer, and then using a tapdenser KYT-2000 (manufactured by Seishin Enterprise Co., Ltd.). The amount of charge was determined by mixing the developer with a conductive iron powder carrier (toner concentration: 3%) and shaking the sample for a predetermined period of time using a "New-Ys shaker" (manufactured by Yayoi Co., Ltd.) to create a triboelectric charge. 2g of toner was placed in a metal container lined with a 350-mesh screen mesh, and nitrogen gas was blown into the nozzle at a pressure of 0.2Kg/ ^cm2 for 3 seconds to scatter the toner from the screen mesh and remove the remaining carrier. The 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】

[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", "Comparison Toner 4"
was evaluated using a U-BixTEN (manufactured by Konishiroku Photo Industry Co., Ltd.) fixing machine modified into a pressure fixing machine (20 kg/cm). Further, "Toner 9" to "Toner 12" were evaluated using a machine called NP-122 (manufactured by Canon). Furthermore, "Toner 13", "Toner 14", and "Comparative Toner 2" were mixed with a conductive iron powder carrier (average particle size 100 μm), and the toner concentration was 3.
% developer. Next, the photoreceptor of U-BixV ₃ R (manufactured by Konishiroku Photo Industry Co., Ltd.) was replaced with an organic semiconductor,
Furthermore, evaluation was performed using a machine in which 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 image quality deteriorated due to its low fluidity, resulting in an uneven image with a lot of fogging. This is because Comparative Toner 3 uses incompatible dimethylsiloxane.
This is thought to be because siloxane was precipitated on the surface of the particles and deteriorated the surface characteristics of the powder. The fixability was evaluated as follows. Using the solid black part (reflection density = 1.0), adjust the load to 2 kg using dyed fabric friction strength tester A-3010 (manufactured by Daiei Kagaku Seimitsu Seisakusho), and use U-Bix
It was rubbed 5 times with Paper 55Kg grade (manufactured by Konishiroku Photo Industry Co., Ltd.), and the change in reflection density was evaluated in percentage. Offset property was determined by measuring the amount of adhesive on the fixing roller after copying 10 sheets of 20cm square solid black area.
We conducted an evaluation. These results are shown in Table-2.

【table】

[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 fixing microcapsule toner comprising an outer wall and a core material, characterized in that at least the core material contains a carboxylic acid-modified silicone oil represented by the following general formula. Microcapsule type toner. (In the formula, x and y are integers, +=2 to 200
It is. R' represents an alkylene group having 2 to 40 carbon atoms. )