JPH11282200A - Capsule toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a capsule toner which shows excellent offset resistance for a heat-pressure fixing method, which can be fixed at a low temp. and which has excellent stress resistance in a developing machine. SOLUTION: This capsule toner consists of a core material containing a core resin and fine wax particles as well as a coloring agent and an electrification controlling material, and a shell material. The volume average particle size (D50) of the toner is 5.0 to 15.0 μm. The core resin has a max. in each region of 1.0×10<3> to 2.0×10<4> and 20.0×10<4> to 80.0×10<4> in the weight mol.wt. distribution and has 25.0 to 55.0 deg.C glass transition temp. (Tg). The fine wax particles have <=5 μm max. particle size. and the weight ratio of the resin to the wax ranges (90 to 70)/(5 to 30). The shell material consists of 30 to 95 wt.% styrene monomers and 70 to 5 wt.% maleic acid monoester and/or fumaric acid monoester monomers and has 50.0 to 75.0 deg.C Tg. The shell material of 0.01 to 2.0 μm thickness covers the core material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a capsule toner used in a copying machine, a printer, a facsimile, and the like utilizing an electrophotographic system.

[0002]

2. Description of the Related Art In an electrophotographic method, for example, an electrostatic latent image is usually formed on a latent electrostatic image carrier made of a photoconductive photoreceptor by charging and exposure, and then the electrostatic latent image is colored. The toner image is developed with particles, and the obtained toner image is transferred to an image support such as transfer paper, and then fixed by heat or pressure to form a visible image. Conventional methods for fixing a toner image include a method of fixing a toner image by heating and melting the toner in a non-contact state, a method of dissolving and fixing the toner with an organic solvent, a method of fixing the toner by pressing, and a method of fixing the toner image. A so-called hot-roller fixing method in which a roller is brought into direct contact with toner and melt-pressed to fix the toner is known, but since heat efficiency is high and high-speed fixing is possible,
The heat roller fixing method is widely used.

However, at the latest, (I) suppression of overheat deterioration of a copying machine, and (II) a warm-up time required to raise the temperature to a temperature at which the heat roller can be fixed after operating the heat roller fixing device. Is shortened, (II
I) minimizing the temperature drop of the heat roller due to heat absorption by the image support such as transfer paper to enable stable and continuous formation of images many times; (IV) miniaturization of copiers From the standpoint of improvement in safety and safety, there is a strong demand for reducing the power consumption of a heater incorporated in a fixing device to enable a fixing process while keeping the temperature of a heat roller lower.

Accordingly, the toner is required to (1) be able to achieve good fixation at a lower temperature, that is, to have excellent low-temperature fixability, and further basically have the following conditions. is necessary. (2) In the heat roller fixing method, which is preferable as a fixing method, a part of the toner constituting the image is transferred to the surface of the heat roller at the time of offset development, that is, fixing, and is transferred again to the next transfer paper. Since the phenomenon that an image is stained is apt to occur, the toner is required to have a property that is less likely to be transferred to a heat roller, that is, to provide an offset resistance. (3) It can be stably present as a powder without agglomeration under conditions of use or storage environment, that is, it has excellent blocking resistance. (4) The toner has good triboelectricity, and the developing process, the transferring process, and the cleaning process are performed well, and a clear image without fog can be obtained. (5) The occurrence of a so-called filming phenomenon in which the toner substance adheres to the surface of the photoreceptor or the surface of the carrier particles is suppressed, and the image can be stably formed many times.

However, conventionally, there has been proposed a technique for improving the low-temperature fixability by using a capsule toner composed of a core material as a toner and a shell material provided so as to cover the surface of the core material. I have. In this type of capsule toner, a low melting point compound or a material having a low Tg is used as a core material in order to improve the melting property at a low temperature. Specifically, the following technology is disclosed. A technique in which a core material is composed of wax (see Japanese Patent Publication No. 49-1588). A technique in which a core material is composed of a polyester crosslinked with a polyvalent metal compound (see Japanese Patent Application Laid-Open No. 58-174957). A technology in which the core is made of a low-melting polyester (JP-A-58-17664)
No. 2). A technique in which the core is composed of a low molecular weight styrene-acrylic resin having a gel fraction of 20 to 70% (see Japanese Patent Application Laid-Open No. 58-176463). A technique in which a core material is composed of an amorphous polyester having a Tg of 60 ° C. or lower (see Japanese Patent Application Laid-Open No. 58-205161). The core material has a Tg of 55 ° C. or less and a gel fraction of 20%.
A technique comprising the above crosslinked vinyl copolymer (see JP-A-58-205161). Tg of core material is 60 ° C
A technology comprising an amorphous polyester having the following acid value (AV) of 10 to 150 (JP-A-58-205163)
Reference). A technology in which a core material is composed of an amorphous polyester and a polyvalent metal compound (Japanese Patent Laid-Open No. 58-205)
No. 164). However, in the above technology, when a heat roller fixing method is applied as a fixing method,
The offset resistance is considerably poor, and the practicality is extremely low.

Further, in the above technology, the performance is improved under the environmental conditions of normal temperature and normal pressure (for example, a temperature of 22 ° C. and 55% RH) as compared with the above technology.
There is a problem that the offset resistance is insufficient, so that the fixing temperature range in which the image can be fixed without occurrence of the offset phenomenon is narrow, and the practicality is still low.

In addition, low temperature and low humidity (for example, a temperature of 10 ° C., 4
Under an environmental condition of 0% RH, the temperature of the image support such as transfer paper is low, so that the melting of the capsule toner tends to be insufficient at the time of fixing, and as a result, the capsule toner having poor fixing constitutes the fixing device. There is a problem that the rollers adhere and accumulate and contaminate the rollers, thereby causing a conveyance failure such as a paper jam and shortening the service life of the rollers.

[0008] As described above, it is a fact that, depending on the capsule toner of the technology, a satisfactory toner has not yet been obtained as a capsule toner for fixing with a heat roller.
This is because it is assumed that the conventional capsule toner is basically applied to the pressure fixing method. That is, the capsule toner is formed so as to be suitable for the fixing method to which the capsule toner is applied. For example, when the capsule toner designed to be applied to the pressure fixing method is applied to the heat roller fixing method, the offset phenomenon may occur. However, it is not always possible to form a sufficient copy image.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object the use of a heat-pressure fixing system such as a heat roller, which has excellent offset resistance and can be fixed at a low temperature. An object of the present invention is to provide a heat and pressure fixing capsule toner having excellent blocking resistance and stress resistance in a developing machine.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, (1) in the weight molecular weight distribution,
It has local maximum values in the ranges of 000 to 20,000 and 200,000 to 80,000, respectively, and has a glass transition temperature (Tg) of 2
A core resin having a temperature of 5.0 ° C. to 55.0 ° C. and wax fine particles having a maximum particle size of 5 μm or less are respectively 90 to 70/70/70.
A core material having a weight ratio of 5 to 30 and further having a colorant and a charge controlling material, and a styrene monomer having a thickness of 0.01 to 2.0 μm and covering the core material of 30 to 95 wt. % And 70 to 5% by weight of a maleic acid monoester and / or fumaric acid monoester monomer, and has a Tg of 5%.
The present invention relates to a capsule toner comprising a shell material having a temperature of 0.0 to 75.0 ° C. and having a volume average particle diameter (D50) of 5.0 to 15.0 μm.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As a monomer for obtaining a core resin and a shell resin used in the present invention, aromatic vinyl monomers such as styrene, α-methylstyrene, halogenated styrene, vinyl Examples thereof include toluene, 4-sulfonamidostyrene, and 4-styrenesulfonic acid, and particularly preferred are styrene monomers; acrylate monomers and methacrylic acid monomers such as methyl (meth) acrylate; Ethyl (meth) acrylate, (meth)
Propyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, hydroxylethyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethyl (meth) acrylate Aminomethyl ester, dimethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, and preferably acrylic acid
n-butyl monomer, n-butyl methacrylate monomer;
Acrylamidoalkylsulfonic acid and / or methacrylamidoacrylsulfonic acid, specifically acrylamidomethylsulfonic acid, acrylamidoethylsulfonic acid, acrylamido-n-propylsulfonic acid,
Acrylamidoisopropylsulfonic acid, acrylamido-n-butylsulfonic acid, acrylamido-s-butylsulfonic acid, acrylamido-t-butylsulfonic acid,
Acrylamidopentanesulfonic acid, acrylamidohexanesulfonic acid, acrylamidoheptanesulfonic acid, acrylamidooctanesulfonic acid, methacrylamidomethylsulfonic acid, methacrylamidoethylsulfonic acid, methacrylamido-n-propylsulfonic acid, methacrylamidoisopropylsulfonic acid, methacrylamide- n-butylsulfonic acid, methacrylamide-s-butylsulfonic acid, methacrylamide-t
-Butylsulfonic acid, methacrylamidopentanesulfonic acid, methacrylamidohexanesulfonic acid, methacrylamidoheptanesulfonic acid, methacrylamidooctanesulfonic acid; itaconic esters such as dimethyl itaconate, dipropyl itaconate, dibutyl itaconate, dioctyl itaconate , Diamyl itaconate, and the like; maleic esters and fumaric esters, for example, maleic esters and fumaric esters having a linear or branched alkyl group having 1 to 8 carbon atoms;
Diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, heptyl maleate, octyl maleate, ethyl butyl maleate, ethyl octyl maleate, butyl octyl maleate, butyl hexyl maleate, pentyl maleate Octyl, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, heptyl fumarate, octyl fumarate, ethyl butyl fumarate, ethyl octyl fumarate, butyl octyl fumarate,
Butylhexyl fumarate, pentyl octyl fumarate and the like; unsaturated carboxylic acids and unsaturated dicarboxylic acids such as (meth) acrylic acid, cinnamic acid, maleic acid,
Fumaric acid, itaconic acid; and others such as 2-vinylnaphthalene, itaconic anhydride, and maleic anhydride, but are not limited thereto.

Further, a polyfunctional monomer and / or a polyfunctional initiator may be used in combination, but it is not always necessary. Examples thereof include a styrene monomer such as divinylbenzene; Multifunctional monomers, for example 1,3
-Butylene glycol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diolate, 1,6-hexanediol diolate,
Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, polypropylene diacrylate, N, N'-methylenebisacrylamide, pentaeristol triacrylate,
Trimethylolpropane triacrylate, tetramethylolpropane triacrylate, 1,4-butanediol diacrylate and the like; methacrylic polyfunctional monomers such as diethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,
5-pentanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate Acrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, polypropylene dimethacrylate, N, N'-methylenebismethacrylamide, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate,
Tetramethylolpropane trimethacrylate, 1,
4-butanediol dimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, aluminum methacrylate, calcium methacrylate, zinc methacrylate, magnesium methacrylate, etc .; For example, t-butyl peroxymethacrylate, t-butyl peroxycrotonate,
Di (t-butylperoxy) fumarate, t-butylperoxyallyl carbonate, tri-t-butyl pertrimellitic acid ester, tri-t-amino pertrimellitic acid ester, tri-t-hexyl pertrimellitic acid, pertrimellitic acid Merritic acid tri-t-1,1,3,3-tetramethylbutyl ester, pertrimellitic acid tree t
-Cumyl ester, pertrimellitic acid tri-t- (p-
Isopropyl) cumyl ester, pertrimesic acid tri-
t-butyl ester, per-trimesic acid tri-t-amino ester, pertrimesic acid tri-t-hexyl ester, pertrimesic acid tri-t-1,1,3,3-tetramethylbutyl ester, pertrimesic acid tri-t-methyl ester t-cumyl ester, per-trimesic acid tri-t- (p-isopropyl) cumyl ester, 2,2-bis (4,4-di-t
-Butylperoxycyclohexyl) propane, 2,2
-Bis (4,4-di-t-hexylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di -T-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di-α-cumylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Butane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) butane; other; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, diallyl chlorendate, ethylene glycol diglycol diglycidyl ether And the like, but are not limited thereto.

The method for obtaining the specific core resin used in the present invention is not particularly limited. For example, a component having a large molecular weight (the maximum value of the molecular weight distribution is 200,000 to 800,000) (Hereinafter referred to as H-form) or a component having a low molecular weight (1.0 of molecular weight distribution).
Component having a maximum value in the range of 1,000 to 20,000 (hereinafter, referred to as L-form)) is subjected to the first-stage polymerization to obtain one component. By dissolving in the monomer composition to obtain the second stage of polymerization, thereby generating the other component,
As a result, a polymer having at least two maxima in the molecular weight distribution curve can be obtained,
If no body is required, one-stage polymerization may be performed.

It is presumed that the polymer obtained by the two-stage polymerization is obtained by uniformly mixing the L-form and the H-form at the molecular level. This two-stage polymerization can be performed by a method such as a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
It is not limited to this.

The core resin used in the present invention has a Tg of 2
5.0 to 55.0 ° C, and in the weight molecular weight distribution,
It has maximum values in the regions of 1,000 to 20,000 and 200,000 to 80,000, respectively. By using a polymer having such a specific molecular weight range as the core resin, it is possible to further improve the low-temperature fixability and the offset resistance. Further, since the specific core resin can be made tough by the H-form, the capsule toner is less likely to be destroyed by friction with the charging member or collision with the photoreceptor, resulting in the generation of fine powder. Can be suppressed, and contamination of the photoreceptor surface can be prevented. Therefore, a clear image without fog can be stably formed many times.

On the other hand, when the maximum value of Mw of the L-form is smaller than the lower limit in the above molecular weight, the storage stability of the capsule toner may be deteriorated. On the other hand, when the maximum value of Mw is larger than the upper limit, At low temperatures. When the maximum value of Mw of the H-form is smaller than the lower limit, the offset resistance and durability of the capsule toner may be reduced. On the other hand, when the maximum value of Mw is larger than the upper limit, the low-temperature fixability of the capsule toner may be reduced. May decrease. The ratio of the H-form in the core resin is preferably 5 to 75% by weight.

The destruction of the shell material and the core material caused by friction with the charging member or collision with the surface of the photoreceptor is mainly caused by the relatively brittle component of the L material in the core material. For this purpose, it is preferred to use a polyfunctional monomer and / or a polyfunctional initiator as its polymerization component. By using these materials to make the L body to a certain degree of toughness, it is possible to suppress the generation of fine powder caused by the destruction of the outer shell and the core material, which is a cause of the filming phenomenon.

Examples of the fine particles of wax in the core material include natural waxes such as ceramic wax, rice wax, sugar wax, urushi wax, beeswax, carnauba wax, white wax and the like, paraffin wax, microcrystalline wax, polyethylene oxide, and polyethylene oxide. Fish wax, ethylene acrylic wax, ethylene vinyl acetate wax, low molecular weight polyethylene wax,
Lipophilic waxes consisting of one or more selected from synthetic waxes such as low molecular weight polypropylene waxes and lanolin, coconut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil,
Examples include fatty acid esters and fats and oils that are liquid at room temperature (25 ° C.) such as palm oil, petrolactam, liquid paraffin, non-oxidized paraffin that is solid at room temperature, non-oxidized microcrystalline wax, and non-oxidized polyethylene.

As a method for producing the wax fine particles, a hot solution obtained by heating and dissolving a lipophilic wax is added little by little to a mixed solution whose lipophilicity has been increased by previously adding the lipophilic wax to water while stirring. Maximum particle size several hundred μm
Is adjusted. By pulverizing this with a pulverizer such as a three-roll mill, a ball mill, a sand mill, and an attritor, stable wax fine particles having a maximum particle size of 5 μm or less can be obtained.

The wax fine particles are added in the form of a dispersion in the step of polymerizing the core resin. The amount is 5-30
Parts by weight. The range of the optimum amount is to satisfy the balance between the storability and the fixing / offset properties when the toner is used. It is desirable that the amount be as small as possible within the above range.

In the present invention, a core material can be manufactured, for example, by the following method. (1) The core resin, the wax, the colorant, and the charge adjusting material for forming the core material are melted and kneaded by, for example, an extruder, cooled, finely ground by a jet mill or the like, and classified. A method of obtaining a core material having a desired particle size. (2) By melting and kneading the core material resin, wax, colorant, and charge adjusting material for constituting the core material by, for example, an extruder, and spraying the mixture in a molten state by a spray dryer or the like, A method for obtaining a core material having a desired particle size. (3) The core material resin, the wax, the colorant, and the charge adjusting material for forming the core material are melt-kneaded by, for example, an extruder, and dispersed in a liquid in a molten state. Of obtaining a core material having a particle size of

The core material contains the core material resin, the wax fine particles, the colorant and the charge controlling material (hereinafter referred to as CCA), and the core material resin is at least 50% by weight or more in the core material. Is preferably contained at a ratio of If this ratio is too small, the offset resistance and durability of the capsule toner may decrease. First, CC
Regarding A, the toner can have an optimal charge amount according to the development system by adding CCA. Such CCA includes a positively charged CCA and a negatively charged CCA,
Examples of the former include nigrosine and fatty acid metal salt derivatives, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, dibutyltin oxide, dioctyltin oxide, dicyclohexyl. Examples include diorganotin oxides such as tin oxide, dibutyltin oxide, dioctyltin borate, and dicyclohexyltin borate. In particular, a positively charged CCA such as a nigrosine-based or quaternary ammonium salt is preferable.

As examples of the negatively charged CCA, organometallic complexes and chelate compounds are effective, and aluminum acetylacetonate, iron (II) acetylacetonate, and chromium 3,5-ditert-butylsalicylate may be mentioned. it can. In particular, metal complexes of acetylacetone (including monoalkyl-substituted and dialkyl-substituted products), salicylic acid-based metal complexes (including monoalkyl-substituted and dialkyl-substituted products) and salts thereof are preferable. Metal salts are preferred. When the above CCA is added to the toner, 0.1 to 10 parts by weight, based on 100 parts by weight of the resin composition for a toner,
More preferably, it is used in an amount of 0.2 to 5 parts by weight. In particular, when used for color image formation, it is preferable to use colorless or pale CCA.

As the colorant, conventionally known dyes and pigments can be used. Specifically, for example, carbon black, magnetite, phthalocyanine blue, peacock blue, permanent red, lake red, rhodamine lake , Hansa Yellow, Permanent Yellow, Benzidine Yellow, Nigrosine Dye (CI No. 50415), Aniline Blue (CI No. 50405), Calco Oil Blue (CI No. azoec Blue 3), Chrome Yellow (CI No. 14090), Ultramarine Blue (CI No. 77103), DuPont Oil Red (CI No. 26105), Orient Oil Red # 330 (CI No. 605
05), quinoline yellow (CI No. 4700)
5), methylene blue chloride (CI No. 5)
2015), phthalocyanine blue (CI No.
74160), malachite green oxalate (C.I.
I. No. 42000), Lamb Black (C.I.
No. 77266), Rose Bengal (C.I.N.
o. 45435), oil black, azo oil black and the like can be used. The addition amount is 3 to 35 parts by weight, preferably 3 to 20 parts by weight, and more preferably 12 parts by weight or less in consideration of a suitable OHP film permeability of a toner image with respect to 100 parts by weight of the resin composition for a toner. Is preferably used, and most preferably 3 to 9 parts by weight.

Next, the shell material will be described. The shell material has a styrene monomer, a maleic acid monoester and / or a fumaric acid monoester monomer as constituents, and has a Tg of 50. 0.0 to 75.0 ° C, particularly preferably 55 to 70 ° C, Mw of 3,000 to 80,
000. The thickness of the shell material is 0.01-2.
The average particle diameter (Dv) is preferably 5.0 to 15.0 μm.

When the Tg of the shell material is in the above range, more excellent low-temperature fixability, offset resistance and durability can be obtained. That is, when the Tg is too small, the shell material becomes soft and the preservability deteriorates. On the other hand, when the Tg is too large, the low-temperature fixability tends to decrease. , (40% RH), sufficient low-temperature fixability may not be obtained.
Further, with respect to the thickness of the shell material, if the thickness is less than 0.05 μm, the manufacturability is difficult, and more uncoated portions are generated, so that the original effect cannot be exhibited.
When the thickness is larger than m, the fixing property at low temperature is not preferable.

The shell material is formed from at least one monomer selected from styrene monomers, acrylate monomers, methacrylate esters, and maleic and monoesters. Among them, as the shell material, a styrene monomer is preferably 30 to 95% by weight, and particularly preferably 4 to 95% by weight.
0 to 95% by weight, and the maleic acid monoester and / or fumaric acid monoester monomer is preferably 5% by weight.
% To 70% by weight, particularly preferably 5 to 50% by weight. When the content ratio of the maleic acid monoester and / or fumaric acid monoester monomer exceeds 70% by weight, storage stability and plasticizer resistance are reduced.

As a method of providing an outer shell on the surface of the core material in the present invention, a coating solution obtained by dissolving the shell material in a solvent is applied to the core material by, for example, a dipping method, a spray drying method, a fluidized bed method or the like. Applying to the surface, heating and drying to remove the solvent by volatilization, curing the applied layer at or after drying to form a coating layer, and fixing the shell material to the core material surface using mechanical impact force A dry capsule method, a spray drying method, a coacervation method, a phase separation method and the like can be preferably used, and an in-situ polymerization method, US Pat. No. 3,338,
No. 991, 3,326,848 and 3,502,582 can be used. For example, in the case of forming a coating layer by a fluidized bed method, in a fluidized bed apparatus, a core material is raised to an equilibrium height by a rising pressurized gas flow, and then by the time the core material falls again. The coating solution is spray-applied, and this spray application is repeated to form an outer shell.

The capsule toner of the present invention uses a surface treating agent. In this regard, by adding the surface treatment agent to the toner, the surface treatment agent is present between the toner and the carrier or between the toners, and the powder fluidity of the developer is improved, In addition, the life of the developer can be further improved. Specific examples include colloidal silica, alumina, titanium oxide, polytetrafluoroethylene, polyvinylidene chloride, polymethyl methacrylate, polystyrene ultrafine particles, and fine powders such as silicone. As trade names, AEROSIL 130, 200, 200V, 2
00CF, 200FAD, 300, 300CF, 38
0, R972, R972V, R972CF, R974,
R976, RX200, R200, R202, R80
5, R812, R812S, TT600, MOX80,
MOX170, COK84, titanium oxide T805, titanium oxide P25 (all manufactured by Nippon Aerosil and Texa), CAB-O-SILL90, LM130, LM
150, M5, PTG, MS55, H5, HS5, LM
150D, M7D, MS75D, TS720, TS61
0, TS530 (above, manufactured by CABOT), etc.
In particular, as the surface area of the surface treatment agent, the specific surface area by nitrogen adsorption by the BET method is 30 m ² / g or more, particularly 50 m ² / g.
Those having a range of ４００400 m ² / g are preferred. The amount of the surface treatment agent to be added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the resin composition for a toner.
The volume average particle diameter (Dv) of the capsule toner is 3.
It is preferably from 0 to 15.0 μm.

[0030]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. Hereinafter, “parts” means parts by weight unless otherwise specified.

Production Example 1 of wax fine particles In a 500 ml beaker, 240 g of Carnauba wax No. 1 (produced by Kato Yoko) and isopropyl alcohol (IPA)
400 g and heated at 80 ° C. to form a uniform hot solution. Next, the above-mentioned hot solution was slowly added little by little to a stirring solution of a mixed solution of 80 g of IPA and 880 g of water in a 2000 ml beaker cooled with ice. Here, a primary dispersion having an average particle diameter of about 100 μm was obtained. This was put into a 10 L experimental ball mill together with magnetic balls and pulverized for 50 hours to obtain stable wax fine particles (fine particles 1) having a maximum particle diameter of 5 μm.

Preparation Example 2 of Wax Fine Particles In a 500 ml beaker, 160 g of rice wax SS (manufactured by Boseau Oil & Fat), 80 g of microcrystalline wax Hi-Mic 1080 (manufactured by Nippon Seiro), and IPA
400 g and heated at 80 ° C. to form a uniform hot solution. Next, the above-mentioned hot solution was slowly added little by little to a stirring solution of a mixed solution of 80 g of IPA and 880 g of water in a 2000 ml beaker cooled with ice. Here, a primary dispersion having an average particle diameter of about 100 μm was obtained. This primary dispersion rapidly precipitated a wax component upon standing. When this is pulverized three times by three rolls, stable wax fine particles having a maximum particle size of 5 μm (fine particles 2)
I got The wax fine particles did not show any change such as coagulation and sedimentation even when left at room temperature for 3 months or more.

Production Example 3 of Wax Fine Particles The same operation was carried out except that lanolin ODL (manufactured by Croda Japan) was used instead of microcrystalline wax in Production Example 2 of wax fine particles.
Stable wax fine particles (fine particles 3) having a maximum particle diameter of 5 μm were obtained.

Preparation Example 4 of Wax Fine Particles Oxidized polyethylene wax A in a 500 ml beaker
160 g of C-629 (made by Allied Chemical) and HNP
-11 (manufactured by Nippon Seiro) 80g and butyl cellosolve 40
0 g and heated at 80 ° C. to form a uniform hot solution. Next, the above-mentioned hot solution was slowly added little by little into a stirred solution of 80 g of butyl cellosolve and 880 g of water in a 2000 ml beaker cooled with ice. Here, a primary dispersion having an average particle diameter of about 100 μm was obtained. This is put into a 10 L experimental ball mill together with magnetic balls, and crushed for 20 hours.
A dispersion in which a wax component of μm was easily precipitated was formed, and the dispersion was further rotated by a ball mill for 30 hours to obtain stable wax fine particles (fine particles 4) having a maximum particle size of 3 μm.

Production Example 1 (for Example) 500 ml of toluene was put into a separable flask having a capacity of 3000 ml equipped with a thermometer, a stirrer, a nitrogen gas introducing tube and a falling condenser, and nitrogen gas was introduced through the nitrogen gas introducing tube. After making the inside of the flask inert atmosphere, the mixture was heated by an oil bath to reach the reflux temperature of toluene. Then
(First Stage Polymerization) An H-form composition comprising 200 g of styrene, 125 g of n-butyl acrylate, 20 g of methacrylic acid, and 0.9 g of benzoyl peroxide was placed in a flask, and allowed to react at reflux temperature for 14 hours. A high molecular weight polymer (H-form) was formed. Next, (second stage polymerization) 382 g of styrene, 35 g of α-methylstyrene, n
The polymerization reaction was carried out while gradually dropping a composition of a low molecular weight component (L-form) comprising 85 g of -butyl acrylate and 42 g of benzoyl peroxide. After the dropping of the composition of the low-molecular-weight component (L-form) was completed, a polymerization reaction was further performed for 4 hours to obtain a low-molecular-weight polymer (L-form). After completion of the reaction, 100 g of the fine particles 1 were added, and toluene as a solvent was distilled off under reduced pressure to obtain a pseudo core material (in the present invention, a resin consisting of only a core resin and a wax is referred to as a pseudo core material). . This is referred to as “pseudo core material A”. This resin A was obtained by gel permeation chromatography (HLC-
802 UR, GMH6 column, manufactured by Tosoh Corporation) in a molecular weight distribution curve of 7.5 × 10 ³ and 2.8 × 1.
Each of them has a maximum value at 0 ⁵ , and Tg is 53 ° C.

Production Example 2 (for Comparative Example) A pseudo core material B was obtained in the same manner as in the production example of the pseudo core material A, except that only the second stage polymerization was performed. The resin B had an Mw of 8.3 × 10 ³ and a Tg of 64 ° C.

Production Example 3 (for Comparative Example) In the production example of pseudo core material A, the monomer composition of the second stage polymerization was 382 g of styrene, 35 g of α-methylstyrene, n
A pseudo core C was obtained in the same manner as in Production Example 1 of the core except that 55 g of butyl acrylate and 42 g of benzoyl peroxide were used. The pseudo core material C had local maximum values at 8.2 × 10 ³ and 3.4 × 10 ⁵ in the molecular weight distribution curve, respectively, and had a Tg of 53 ° C.

Production Example 4 (for Comparative Example) In the production example of pseudo core material A, the polymer obtained by performing only the first stage polymerization was isolated to obtain pseudo core material D. Mw was 2.4 × 10 ⁵ and Tg was 14 ° C.

Production Example 5 (for Example) A pseudo core material E was obtained in the same manner as in the production example of the pseudo core material A, except that the fine particles 2 were used instead of the fine particles 1. Mw was 3.4 × 10 ⁵ and Tg was 52 ° C.

Production Example 6 (for Example) A pseudo core material F was obtained in the same manner as in the production example of the pseudo core material A, except that the fine particles 3 were used instead of the fine particles 1. Mw was 2.9 × 10 ⁵ and Tg was 52 ° C.

Production Example 7 (for Example) A pseudo core material G was obtained in the same manner as in the production example of the pseudo core material A, except that the fine particles 4 were used instead of the fine particles 1. Mw was 3.1 × 10 ⁵ and Tg was 54 ° C.

Production Example 8 (for Examples) A pseudo core material H was obtained in the same manner as in the production example of the pseudo core material A, except that the fine particles 5 were used instead of the fine particles 1. Mw was 3.4 × 10 ⁵ and Tg was 51 ° C.

Production Example 9 (for Example) A pseudo core material I was obtained in the same manner as in the production example of the pseudo core material A, except that 60 g of the fine particles 1 were used. Mw was 3.5 × 10 ⁵ and Tg was 56 ° C.

Production Example 10 (for Example) A pseudo core material J was obtained in the same manner as in the production example of the pseudo core material A, except that 250 g of the fine particles 1 were used. Mw was 3.9 × 10 ⁵ and Tg was 58 ° C.

Example A core material was produced from the pseudo core materials obtained in Production Examples 1 to 4 and Production Examples 1 to 10 of the wax fine particles, and the shell material was covered and encapsulated, and a capsule toner was produced and evaluated. (1) Manufacture of core material 1) 88 parts of the pseudo core material A and CB as a coloring agent
(Oil absorption 80.7 ml DBP / 100 g, pH 3.2,
7 parts of BET specific surface area 108 m ² / g), 5 parts by weight of polypropylene “High Wax 105P” (manufactured by Mitsui Chemicals, Inc.), and a charge control material (“Bontron S-3” manufactured by Orient Chemical)
4) 1 part was mixed with a V-type blender, then melt-kneaded with a twin-screw kneader, cooled, crushed with a hammer mill, finely crushed with a jet mill, and then classified with an air classifier. A core material having a particle size of 3 to 30 μm was obtained. This is referred to as material 1. 2) A material 2 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material B was used. 3) A material 3 was obtained in the same manner as in the preparation of the material 1 except that the pseudo core material C was used. 4) A material 4 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material D was used. 5) A material 5 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material B was 30 parts and the pseudo core material D was 58 parts. 6) A material 6 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material B was 58 parts and the pseudo core material D was 30 parts. 7) A material 7 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material E was used. 8) A material 8 was obtained in the same manner as in the preparation of the material 1 except that the pseudo core material F was used. 9) A material 9 was obtained in the same manner as in the preparation of the material 1, except that the pseudo core material G was used. 10) A material 10 was obtained in the same manner as in the preparation of the material 1, except that the similar core material H was used. 11) A material 11 was obtained in the same manner as in the preparation of the material 1, except that the similar core material I was used. 12) A material 12 was obtained in the same manner as in the preparation of the material 1, except that the similar core material J was used.

(2) Shell Material Shell Material 1; Styrene-monobutyl maleate copolymer (copolymerization weight ratio = 75:25, Mw 5,400, Tg56)
C) Shell material 2: Styrene-monobutyl maleate copolymer (copolymer weight ratio = 85:15, Mw 5,500, Tg 64)
C) Shell material 3: Styrene-monobutyl maleate copolymer (copolymer weight ratio = 55:45, Mw 5,550, Tg 42)
° C) (for Comparative Example) Shell material 4: styrene-monobutyl maleate copolymer (copolymerization weight ratio = 75:25, Mw 35,500, Tg59)
C) Shell material 5; Styrene-monobutyl fumarate copolymer (copolymerization weight ratio = 75:25, Mw 5,800, Tg53)
℃)

(3) Step of Encapsulation To 500 parts of the emulsified dispersion of the shell material 1, 300 parts of the above material 1 was added and sufficiently dispersed, and then the inlet temperature was 180 ° C. and the outlet temperature was 6
Spray drying was performed at 0 ° C. to form an outer shell made of the above shell material on the surface of the core material to obtain a capsule toner powder.
The thickness of the shell material was 1.2 μm on average. To 100 parts of the capsule toner powder, 0.3 part of a surface treating agent (BET specific surface area: 130 m ^{2 /} g, pH 4.5) was added and mixed to obtain a capsule toner according to the present invention. This is referred to as toner 1. Hereinafter, for toner 2 and later, Table 1
In the same manner as in the toner 1 with the combination shown in
Toner 23 was obtained.

(Measurement of Molecular Weight of Resin) The molecular weight of the resin was measured by gel permeation chromatography (GPC) using commercially available monodispersed standard polystyrene as a standard, tetrahydrafuran as a solvent, and a refractometer as a detector. I asked. In measuring the molecular weight of a sample, a measurement condition in which the logarithm and the count number of the molecular weight of the calibration curve prepared by using several kinds of monodisperse polystyrene standard samples are included within a linear range is selected. . Note that the reliability of the measurement results was determined by the NBS 70 measured under the above measurement conditions.
6 polystyrene standard sample (Mw = 28.8 × 10 ⁴ , M
n = 13.7 × 10 ⁴ , Mw / Mn = 2.11) Ratio M
It is confirmed that the value of w / Mn is 2.11 ± 0.10. As the GPC column to be used, any column may be adopted as long as the above conditions are satisfied. Detector: SHOdex RI SE-31 Solvent: Tetrahydrofuran column: A-80M x 2 + KF-802 Flow rate: 1.2 ml / min Sample: 0.25% THF solution

[0049]

[Table 1] 疑 Pseudo core material of toner capsule Shell material Film thickness Volume average particle size (core resin) (μm) (μm) ───────────────────────────────────ト ナ ー Toner 1 Material 1 (A) Shell material 1 1.2 8.1 Toner 2 Material 2 (B) Shell material 1 1.0 8.6 Toner 3 Material 3 (C) Shell material 1 1.0 8.2 Toner 4 Material 4 (D) Shell material 1 1.1 8.4 Toner 5 Material 5 (B + D) Shell material 1 1.0 8.7 Toner 6 Material 6 (B + D) Shell material 1 1.2 8.6 Toner 7 material 7 (E) Shell material 1 1.2 8.3 Toner 8 Material 8 (F) Shell material 1 1.4 8.9 Toner 9 Material 9 (G) Shell material 1 0.9 9.2 Toner 10 Material 1 ( A) Shell material 1 0.8 9.4 Toner 11 Material 1 (A) Shell material 1 1.0 8.1 Toner 12 Material 1 (A) Shell material 1 1.1 7.9 Toner 13 Material 1 (A) Shell material 2 1.0 8.5 Toner 14 Material 2 (B) Shell material 2 0 8.6 Toner 15 Material 3 (C) Shell material 2 1.1 8.5 Toner 16 Material 1 (A) Shell material 3 1.2 8.6 Toner 17 Material 2 (B) Shell material 3 1.1 8 .2 toner 18 material 3 (C) shell material 3 1.1 8.1 toner 19 material 1 (A) shell material 4 0.9 8.6 toner 20 material 2 (A) shell material 4 1.0 7.8 Toner 21 Material 1 (A) Shell material 5 1.2 7.9 Toner 22 Material 2 (B) Shell material 5 1.2 8.6 Toner 23 Material 1 (A) None 0.0 7.9 mm ────────────────────────────────

(4) Actual Photographic Test An electrostatic latent image is formed and developed by a copying machine modified from a commercially available electrophotographic copying machine using the above-mentioned developer, and the obtained toner image is transferred onto a transfer paper. The following items were evaluated without performing a real test to form a copied image by fixing with a heat roller fixing device.

Minimum Fixing Temperature (Fixing Property) After an unfixed image is formed by the above copying machine, a heat roller having a diameter of 30φ and a surface layer formed of Teflon (polytetrafluoroethylene manufactured by DuPont) and a silicone rubber layer formed on the surface layer The heat roller fixing device including a pressure roller formed of “KE-1300RVT” (manufactured by Shin-Etsu Chemical Co., Ltd.)
A toner image of a sample toner transferred to a transfer paper of 4 g / m 2 was transferred to a heat roller at a linear velocity of 70 mm / sec and a linear pressure of 0.8.
The operation of fixing with a nip width of 4.9 mm / kg / cm is repeated at each temperature by setting the set temperature of the heat roller in steps of 5 ° C. within a range of 100 ° C. to 240 ° C. The rubbing was performed with a Kimwipe, and a minimum fixing temperature (Tf) was defined as a minimum setting temperature for a fixed image showing sufficient rubbing resistance. The heat roller fixing device used here does not have a silicone oil supply mechanism. The environmental conditions were normal temperature and normal pressure (temperature 20 ° C., relative humidity 60%). ×; 180 ≦ Tf <240 (° C.) Δ; 145 ≦ Tf <180 (° C.) ○; 110 ≦ Tf <145 (° C.); Tf <110 (° C.)

Offset occurrence temperature (offset property) The measurement of the offset occurrence temperature is similar to the measurement of the above-mentioned minimum fixing temperature.
The toner image is transferred and the fixing process is performed by the above-described heat roller fixing device. Then, a blank transfer sheet is sent to the heat roller fixing device under the same conditions, and whether or not toner stain occurs on the transfer sheet is visually observed. The operation was repeated while the set temperature of the heat roller of the heat roller fixing device was sequentially increased, and the lowest set temperature at which toner contamination occurred was taken as an offset occurrence temperature (Tof), and displayed based on the following range standard. The environmental conditions are normal temperature and normal pressure (temperature 22 ° C., 55%
RH). ×; Tof <190 (° C.) Δ; 190 ≦ Tof <210 (° C.) ○; 210 (° C.) ≦ Tof

Blocking resistance (storability) The blocking resistance was tested at a temperature of 55 ° C. and a relative humidity of 6
It was left for 1 day under 0% environmental conditions, and it was determined whether or not agglutinates were formed in the toner. When no agglomerates were found, it was evaluated as “「 ”. And

Image Quality The actual copying test was continuously performed 30,000 times by the above copying machine, and the sharpness of the copied image at the initial stage of image formation and after 30,000 times was examined. The evaluation was evaluated as "O" for good, and "△" for practical but not practical.
Those that were inferior and had problems in practice were marked with "x".

Cleaning Performance A 30,000 actual copying test was continuously performed by the above copying machine, and every time the number of copying reached 5,000, the surface of the photosensitive member cleaned by the cleaning blade was visually observed. It was determined based on the presence or absence of attached matter. In the evaluation, good samples were evaluated as “○”, those which were not good but were at a practical level were evaluated as “△”, and those which were inferior and had practical problems were evaluated as “x”. Table 2 shows the evaluation results.

[0056]

[Table 2] ─────────────────────────────────── Toner fixing property Offset blocky Image quality Cleaning property性 1 ○ ○ ○ ○ ○ 2 (Comparative example) ○ × ○ × × 3 (Comparative example) △ ○ △ △ ○ 4 (Comparative example) ◎ ○ × × × 5 ○ ○ ○ ○ ○ 6 ◎ ○ ○ △ ○ 7 ○ ○ ○ ○ ○ 8 ○ ○ ○ ○ ○ 9 ○ ○ ○ ○ ○ 10 ○ ○ ○ ○ ○ 11 ○ ○ ○ ○ ○ 12 ○ ○ ○ ○ ○ 13 ○ ○ ○ ○ ○ 14 (Comparative example) ○ × ○ × × 15 (Comparative example) △ ○ △ △ △ 16 (Comparative Example) ○ ○ × △ △ 17 (Comparative example) ○ × × × × 18 (Comparative example) ○ ○ ○ × × 19 ○ ○ ○ ○ ○ 20 (Comparative example) ○ ○ × × × 21 ○ ○ ○ ○ ○ 22 (Comparative example) ○ △ × × × 23 (comparative example) △ ○ △ △ △ ───────────────────────────────────

[0057]

According to the present invention, in a heat and pressure fixing system such as a heat roller, a heat and pressure fixing capsule which is excellent in offset resistance, can be fixed at a low temperature, and is also excellent in blocking resistance and stress resistance in a developing machine. A toner was obtained.

Claims (1)

[Claims] (1) a weight-molecular weight distribution of 1.00 to
It has local maximum values in the regions of 20,000 and 200,000 to 80,000, respectively, and has a glass transition temperature (Tg) of 25.0 ° C.
Core resin having a temperature of ５５55.0 ° C. and a maximum particle size of 5 μm
The following wax fine particles were respectively 90 to 70/5 to 30
A core material containing a colorant and a charge controlling material in a weight ratio, and 30 to 95% by weight of a styrene monomer and 0.01% to 2.0 μm of the styrene monomer to cover the core material with a thickness of 0.01 to 2.0 μm. Acid monoester and / or fumaric acid monoester monomer in an amount of 70 to 5% by weight and a Tg of 50.0 to 7
It is made of a shell material at 5.0 ° C, and has a volume average particle size (D50)
Is from 5.0 to 15.0 μm.