JPS62205366A - Capsule toner - Google Patents

Abstract

PURPOSE:To obtain the titled toner having excellent durability and fixing property under a pressure, and electrostatic charge controlling property and capable of giving a good image by using a vinyl polymer having a prescribed mol.wt. at an outer shell of the titled toner contg. a core material particle, an outer shell material, and an inorg. fine particle near to a surface of the core material particle. CONSTITUTION:The titled toner contains the core material particle, and the outer shell formed from an org. solution phase by a phase separation method and the inorg. fine particle near to the core material particle. The main component of the outer shell is composed of a vinyl polymer, and the ratio of Mw/Mn (Mw is the weight average mol.wt. and Mn is the number average mol.wt.) is >=3.5, preferably 5.0-30. The polymer may contain a kind of the polymer, a mixture of the polymers having different mol.wt. respectively, or may be mixed with an another resin by <40wt%. the core substance is obtd. by dispersing a coloring agent, optionally together with a magnetic powder in the resin. Al2O3, TiO2, and another powder are used as the inorg. fine powder.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a toner used to develop an electrical latent image in electrophotography or electrostatic printing, and particularly to a toner used in pressure fixing and/or electrostatic printing. This invention relates to a capsule toner suitable for low temperature heat fixing.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297.69
Specification No. 1, Japanese Patent Publication No. 42-23910 (U.S. Patent No. 3,666.363), and Japanese Patent Publication No. 43-247
Publication No. 48 (U.S. Patent No. 4,071,361)
Many methods are known, as described in et al., but generally, photoconductive substances are used and various means are used to
Forming an electrical latent image on a photoreceptor, then developing the latent image using toner, transferring the toner image to a transfer material such as paper as necessary, and then fixing it to obtain a copy. The process is taken.

In order to fix the toner image, a heating chamber 71 method is generally used in which the toner image is heated and melted using an infrared heater or a heated roller, and then fused and solidified to the support. For reasons such as ffj′g, heating is not necessary or the wood quality has been reduced.
The pressure fixing method using rigid rollers is gradually changing.In particular, this pressure fixing force type eliminates the risk of burning the copy sheet, and there is no waiting time once the copying machine is turned on. The projection is irritating, the high-speed joseki is i+f capable,
There are many advantages such as the simplicity of the 7-place device.

Specifically, there are 8 types of toners that can be fixed by pressure, in which the constituent resin has properties suitable for pressure fixing.
The development of resins suitable for this [1] is actively being carried out. However, Naka JZ) has excellent pressure fixing properties, does not cause offset phenomenon to the pressure roller, and has stable developing and fixing performance even after repeated use, and can be applied to carriers, metal sleeves, and photoreceptor surfaces. A good practical pressure fixing method that does not cause adhesions, agglomeration or caking during storage, and is storage stable.

In particular, add f'E? [Waka1'1's point retsu ta (', to,
Determination] i: M has g questions.

In order to satisfy the various characteristics required for such pressure fixing 1-yt- by layering 1.10-particles,
A variety of capsule-shaped capsules with a shell of fecal resin have also been proposed. For example, there are 4
'rKoshō 54-8104''-3-(USA!tAfilI
No. 3.788.994) No. 2, 'The eave as seen: A capsule membrane with Kamonogei as its core... or (
Dimensions, 1l14: quality resin soluble core capsule)・Nursing, but pressure foot 2''I insufficiency, O:lack]・phenomenon, there are many unresolved problems such as photoreceptor contamination, and it is not put into practical use. has not yet been reached.

Similarly, with capsule toners such as those mentioned above, the molecular weight of the resin used for the shell material has not been studied, so the strength of the shell material is often insufficient, and the durability as a developer is poor. Poor [7, lTj staining and melting γi on the surfaces of the developing sliver, photoreceptor, and gearbox due to peeling of the shell material.]
[Jiya 1. In addition, to the extent that the strength of the shell is satisfied, b
If the thickness of each film is increased, the toner fixation +1 will be extremely low.

According to research by Nagisa et al., the capsule membrane surface tends to become slippery when a low molecular weight vinyl polymer is used as the main component of the capsule toner shell. Although the initial image quality is good, the strength as a shell material is weak, so as mentioned above, there are major problems in terms of durability. On the other hand, when a high-density vinyl polymer is used, the durability is 1-1, but the surface of the capsule membrane is
It tends to produce many protrusions, resulting in poor image quality due to unstable marketability of toner particles, looseness of the protruding shell material that occurs when adding a fluid embedding agent, and poor image quality on the developing sleeve. 71. 1. The problem of further non-uniformity.

Furthermore, when a vinyl polymer with a wide molecular weight distribution ranging from low molecular weight to high molecular weight is used, the encapsulation manufacturing conditions become difficult, resulting in the generation of particles consisting only of shell material containing no molecules or particle aggregation. Since there is a problem that agglomeration and multinucleation due to oxidation are difficult, there is a limit to the molecular distribution of the polymer that can be used to form the shell material.

[Problems to be Solved by the Invention] One object of the present invention is to provide a pressure-fixable capsule membrane which is free from the above-mentioned drawbacks by the latest improvement. Another objective is to provide a capsule I-ner with fewer restrictions on the distribution of the polymer forming the uppermost layer.

Furthermore, even when taking multiple shots, it maintains excellent image quality.
No contamination or adhesion to the surfaces of the developing sleeve, photoreceptor, carrier, etc.] [Pressure fixing performance] Excellent resistance to stains, and good fixing performance at a lower pressure than before, compared to paper feeding Our goal is to provide capsule toner.

Furthermore, another object of the present invention is to provide a pressure fixable capsule toner exhibiting LI-like charge controllability and stable charge controllability.

Furthermore, another object 1-1 of the present invention is to prepare the magnetic fine particles with gold stone [
7th, 1 for -component type developer.Even when it is 1/2, good pressure standard +1 and development +1 are small, 11 electrostatic,
The purpose of the present invention is to provide a pressure constant R1 type toner that can be transferred at a constant rate.

A further object of the present invention is to provide a capsule toner for fixing with a pressure roller that may be heated at a low temperature.

[Means and effects for solving the problem] The present inventors have proposed that in a capsule toner consisting of core particles and a shell material covering the core particles, inorganic particles are added near the surface of the core particles.
The main distillate component is a vinyl polymer and the ratio of its weight average molecular weight Mw to several thousand equivalent weight Mn (M w 7
It has been found that a good capsule toner can be obtained by coating with a shell material having an M n ) of 3.5 or more. In other words, by making the inorganic particles exist near the surface of the core particle, the surface shape of the core particle becomes an irregular surface, and the organic solution phase becomes difficult to form in a phase separation method or an encapsulation method using a spray dryer. When the polymer particles for forming the outer shell are precipitated on the surface of the core material, the polymer side starts to precipitate first because the polymer side of the polymer has lower solubility in the solvent. The reason for this is that the surface of the core particles has a finely uneven structure, which increases the contact area between the core particles and the shell material, and in addition, the capillary phenomenon of the finely uneven structure causes a strong penetrating force to act on the four parts of the core particle surface. Therefore, it firmly sticks to the surface of the core material and has very good adhesion with the core material particles. After the polymer side precipitates and fills all four parts of the core material surface, the low molecular side starts to precipitate.

In this case, the low molecular weight side has a strong affinity with the solvent, so even in the precipitated state, it adheres to the surface of the core material while still containing a considerable amount of solvent, and then the solvent gradually escapes, resulting in the final product. The capsule toner has a smooth surface. Therefore, the resin forming the outer shell has a wide molecular weight distribution M w
It is preferable to use a resin with a large value of /Mn.

In addition, the inorganic particles present near the surface of the core material act as fillers for the shell material, greatly increasing the strength of the shell material. Therefore, even if the shell material has a thin film thickness, the capsule toner is extremely unlikely to be destroyed during agitation or cleaning in a developing machine, and on the other hand, during fixing, the thin film thickness does not impede fixing performance. Further, according to the present invention, the polymer resin for shell material shape has a wide molecular weight distribution (M w / M
Even if a polymer with a large n value is used, free shells may occur on the surface of the core particle due to poor adhesion of precipitates on the polymer side with low solubility to the core particle. Since it is suppressed by the penetrating force of capillary action due to the fine structure of the particles, it can be used in a phase separation method from an organic solution phase and an encapsulation method using a spray dryer method. In the present invention, a vinyl polymer or copolymer for forming the outer shell having a wide range of molecular weight in, that is, a material having a large M w 7M, n can be preferably used.

The present invention will be explained in more detail below. In the following description, "%" and "part" expressing quantitative ratios are based on weight unless otherwise specified. Further, the core material of the capsule toner of the present invention is basically formed by dispersing a colorant and, if necessary, magnetic powder into fine particles in a resin as a pressure fixing component. As the resin constituting the core material, soft solid materials that exhibit favorable fixing properties can be used, such as waxes (beeswax, carnauba wax, paraffin wax, microcrystalline wax, etc.), higher fatty acids, etc. (stearic acid, palmitic acid,
lauric acid, etc.), higher fatty acid metal salts (aluminium stearate, lead stearate, barium stearate,
Magnesium stearin, zinc stearate, zinc balmitate, etc.), higher fatty acid derivatives (methyl hydroxystearate, glycerol monohydroxystearate 1, etc.), polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polyisobutylene, poly ethylene tetrafluoride, etc.) and their chemical reaction products with amino group-containing monomers, olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene - Methacrylic ester copolymer, ethylene-vinyl chloride copolymer, ethylene-acetate vinyl copolymer, ionomer resin, etc.), styrene resin (low molecular weight polystyrene, styrene-butadiene copolymer, (monomer/polymer - Gravity ratio 5-30: 95-70), styrene-acrylic compound copolymer, etc.), epoxy resin,
Polyester resin (l11 value 10 or less), rubbers (inbutylene rubber, nitrile rubber, chloride rubber J1, etc.), polyvinylpyrrolidone, polyamide, coumaron-indene resin, methyl vinyl ether-anhydrous maleic butyrohair polymer,
There are maleic acid-modified phenol resins, phenol-modified terpene resins, silicone resins, etc., and these can be used alone or in combination.

The core material of the capsule toner of the present invention generally contains various dyes and pigments as colorants.

Examples of such dyes and pigments include carbon black, nigrosine dye, lamp black, and sudan black SM.
, First Yellow G, Benzidine Yellow, Hikment Yellow, Indofurth H-Orange, Irgazine Red, Rose, Troanilini/・L/Redto 1
1. /Ijin Red, Car Sun FB, Permanent-
Bordeaux FRR, Pigment ψ 1st/Nji R, Linur San Red 2G, Rake Sen Red C, Rhodamine FB,
Rhodamine B Lake, Methyl Yuvio Red B Lake, Phthalosia, Nin゛ Blue, Pigment Blue, Brilliant φ Green B, Phthalocyanine Green, Oil Yellow GG, Sahon, First Yellow GG,
Kaya set Y963, Kaya set YG, Sumipunst φ
Yellow GG, f Bonfast Orange RR, Oil・
Scarlet, Sumiplast Ori/Nji G, Orazole φ Brown B, Pomelo First Scarlet L-G G
, Eisensviron ++1/Tsudo-BEH, Oil Pink OF, etc. can be applied. These colorants are -・2 in the shell.
Used to obtain capsule toner for component developers,
It is preferable to add it in an amount of 0.5 to 15% by weight based on the core material binder.

Further, in order to use the capsule toner of the present invention as a one-component magnetic 1.toner, magnetic powder may be contained in the core material. Such magnetic powder is a substance that is magnetized when placed in a magnetic field, and includes powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. This magnetic powder may also be used as a coloring agent. The content of this magnetic powder is preferably in the range of 50 to 90 parts per 100 parts of the total resin in the core material.

The core material of the capsule toner of the present invention is obtained by melt-kneading the above components, granulating them in hot water containing a hardly soluble inorganic dispersion stabilizer, or granulating them using a spray dryer, and then classifying them as necessary. By doing this, the volume/P-average particle size is 5~
Prepared as 20 liter microparticles.

In the method of making inorganic particles exist near the surface of the core particle of the capsule toner of the present invention, inorganic fine particles are externally added to W.
The fine inorganic particles may be attached to the surface of the core material particles, or after attachment, a portion of the particles may be rolled out by heat treatment.

Examples of inorganic fine powders include alumina, titanium dioxide, barium titanate, magnesium dicinate, butycalcium titanate, strontium titanate, zinc oxide, silica sand, 1/-1 cloud [, wollastonite, diatomite, Various inorganic oxide pigments, chromium oxide, cerium oxide, red iron oxide, -
1:.

Examples include powders and particles of antimony oxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silica fine powder, silicon carbide, silicon nitride, boron carbide, tungsten carbide, titanium carbide, and the like. Non-magnetic particles are usually used as the inorganic particles, but magnetic particles can also be used.

These inorganic fine powders preferably have hydrophobic or etc. are good.

In addition, as inorganic fine particles, they are smaller than thought particles.
3T sheets have a specific surface area of 50 to 400 m'/g by the BET method using N2 adsorption.
Those within the range of are preferably used. The amount added is o, oi to 60% by weight based on the weight of the core material, preferably 0.1
It is used in an amount of 1 to 10% by weight, particularly preferably 1 to 10% by weight. By such an external addition mixing operation, the inorganic fine particles are attached to the core material particles in a state where they are embedded in the surface or surface layer.

The capsule toner of the present invention is composed of core particles as described above and an outer shell that covers the core particles, and the main component of the outer shell is a vinyl polymer and has a weight average molecular weight (M w ).
and number average molecular weight (M n ) (M w / M n
) is 3.5 or more (more preferably 5,0 to 30), it may be a single polymer or a mixture of two or more different polymers having different molecular weights. Number average molecular weight (M n )
2000~30000, preferably 5000~
A range of 20,000 is used. If less than 2000 is used, the strength of the shell material will be weakened, and if less than 30
,000 or more, the capsules tend to aggregate during encapsulation.If a polymer with Mw/Mn of 3.5 or less is used, the encapsulation surface will not be smooth and the copied image will be scattered. Recovery is likely to occur.

The above-mentioned vinyl polymer can be obtained as a homopolymer or a copolymer of two or more types of vinyl monomers shown below. That is, styrene, 0-methylstyrene, m-methylstyrene,
p-Methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p - Consisting of styrene and its derivatives such as -tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, etc. Styrenic monomers: Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; Vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc.; Vinyl acetate, vinyl propionate, benzene Vinyl esters such as vinyl methacrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylate
α-methylene fatty acid monocarboxylic acid esters such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, α-chloromethacrylate, methylmaleic acid, maleic acid ester; methyl acrylate, ethyl acrylate, n-butyl acrylate , isobutyl acrylate, propyl acrylate, acrylate esters such as Mn-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl arylate, 2-chloroethyl acrylate, phenyl acrylate;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole,
- N-vinyl compounds such as vinylpyrrolidone; vinylnaphthalenes; acrylonitrile, methacrylaterile,
Acrylic acid or methacrylic acid derivatives such as acrylamide; tertiary amino group-containing vinyl hexamers such as dimethylamine ethyl methacrylate, dimethyl phenyl acrylate, dimethylamine propylacrylamide, and diethylaminoethyl methacrylate.

Among these, a copolymer of a styrene monomer and a tertiary amino group-containing vinyl monomer, which also provides excellent charge controllability, is particularly preferably used. Styrenic monomer and third
The preferred copolymerization ratio with the amino group-containing vinyl monomer is:
The molar ratio is 1:O, in the range of O1 to 0.5.

A vinyl polymer that satisfies the above molecular weight conditions can be produced by controlling monomer polymerization conditions, polymer fractionation method, or both (by using II).Polymerization methods include , Bulk polymerization〃4, Solution polymerization method, Suspension Φ polymerization〃1, Emulsification method, etc., polymerization is carried out by adjusting the concentration of 1,000 ml, initiator concentration, chain transfer agent concentration, etc. , living polymerization using an on-initiator, and cassette A-on polymerization method. Typical methods for separating polymers include the Aifi fractionation method, the fractional dissolution method, the 8-fraction fractionation method, and the GPC method.

In addition, Hn and Bodw/Mn in the present invention are expressed as 'AI!' by GPC (gel permeation chromatography) υ based on the following AlI3 standard 1 1
15 taste the specified value.

In other words, using Showdex 80M as color 1,
1. tetrahydrofuran at a temperature of 40°C. m f
The sample polymer dissolved in 0.1% tetrahydrofuran 7a was added at a flow rate of 300 to 500 ml 11'.
Take measurements. When measuring the molecular TiX- of a sample, the fractional early distribution of the sample is determined by the fact that the molecular j110 logarithm and count number of the first line are within the 7j line region. Set it so that Also, in this i+lil constant, I!
+su, i,) Soriya 1 beam, >4\ article 11 Al11
Release '1. .

NB5706 Boris thousand mark W, i sample Bodhisattva W/'
Since the material n is 2.11±0.10, it is +j? l
do. The measured Tjl was measured using a 150C type GPC device manufactured by Waters No. It is also possible to combine other molecule 41 vinyl polymers or other resins.

For example, examples of resins that can be added include resins made of the following monomers. Styrene, p-chlorostyrene, p-dimethylamino-methylene and other substituted styrene; methyl acrylate, /ethyl acrylate,
Acrylic butylene, methyl methacrylate, methacrylic cochyl, butyl methacrylate 5, methacrylic acid N.

Esters of acrylic acid or methacrylic acid such as N-dimethylaminoethyl ester; maleic anhydride or maleic anhydride halfester, half amide or diester imide; nitrogen-containing vinyl such as vinylpyridine and N-vinylimidazole; vinyl; Vinyl acetals such as formal and vinyl butyral; vinyl chloride,
Vinyl monomers such as acrylonitrile and vinyl acetate;
Vinylidene monomers such as vinylidene chloride and vinylidene fluoride;
It is a fin monomer. In addition, polyester, polycarbonate, polysulfonate, polyamide, polyurethane, polyurea, epoxy resin, rosin, modified rosin,
Homopolymers or copolymers such as terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, melamine resins, polyether resins such as polyphenylene oxide, or 1,000-onythyl resins. ,
Or you can use 4 combinations.

Various known encapsulation techniques can be used to fold the capsule toner having an outer shell made of these polymers. For example, spray drying method, phase separation method, etc. can be suitably used, as well as U.S. Pat. Method U described in No. 582 can also be used, but a method of phase separation from an organic solution phase is particularly preferred.

The thus obtained capsule toner of the present invention generally has an outer shell with a thickness of 0.05 to 0.5 +1, and is a microcapsule with an average particle size of 3 to 181t.

[Example 1] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, "bu" means "jutobu".

Example 1 The core material was composed of 30 parts of a chemical reaction product obtained by reacting 5 g of dimethylamino]delmethacrylate per loog of paraffin wax, 20 parts of polyethylene wax, 20 parts of paraffin wax, 30 parts of carnauba wax, and a particle size of 0.
Adding 80 parts of 2g of magnetite, melting and mixing at 120°C, granulating with a spray dryer, and performing dry classification to obtain a volume average particle size of 10.0. It is. A spherical product was obtained.

1-Particle distribution per 100 parts by weight of wet silica Psil E) 0
．． A mixture of 6 parts by weight was stirred for 60 seconds using a Henschel mixer with a 6 scale dial to stick silica on the particle surface to prepare core particles.

Number average molecular weight M n = 8267, M w /
100 parts by weight of the obtained core particles were dispersed in a dimethylformamide solution in which 15 parts by weight and 2B parts of a styrene-dimethylaminoethyl methacrylate (molar ratio 90/10) copolymer having a value of M n = 5.99 was dissolved. Then, by gradually adding water and causing phase separation, encapsulated particles coated with a film thickness of about 0.351 L were obtained.

Next, 0.8 g of wet silica Psil E) was externally added and mixed to 100 g of the encapsulated particles using a coffee mill to obtain a developer. When this toner was observed using a scanning electron microscope, it was found that the surface of the outer shell of the toner had few irregularities, was smooth, and no free shell material was observed.

When 9 g of iron powder (200 to 300 mesh) was mixed with 1 g of this developer, the amount of triboelectric charge was measured by a known measuring method, and it was found to be +11 gc/g. This developer was applied to a developing machine having a magnetic sleeve to develop a latent image with a negative electrostatic charge, which was then transferred onto high-quality paper. When the transfer paper carrying the toner image was passed through a pressure fixing machine consisting of two wooden pressure rollers capable of applying pressure from both ends, it was transferred at a speed of 115 mm/sec to 14 kg.
At a linear pressure of / cm, almost perfect fixing was achieved.

The image density was 1.35, and a clear image without fog was formed, which was good.

Furthermore, after an 8-hour idling durability test in a developing machine at a speed of 115 mm/see, the image was printed again, and the image density was 1.5, with no change in image quality, which was excellent. Durability was recognized. The amount of triboelectric charge of the developer at this time is +12
．． There was no contamination or fusion on the sleeve surface, and when the toner surface was observed using an electron microscope, no peeling of the outer shell wall occurred.

Comparative Example 1 The core material of Example 1 was converted into Hn-5308, Bodhisattva W/Bond =
Encapsulation and external addition treatment were carried out in the same manner as in Example 1 using only the styrene-dimethylaminoethyl methacrylate (molar ratio 90/10) strong electric composite having a value of 2.30,
A developer was obtained.

The surface of the outer shell of this]・ner was smooth with no irregularities, and the amount of triboelectric charge was +9.8 gC/g. Using this developer, a test similar to that in Example 1 was conducted, and the initial image had similar fixing properties and image quality, and the image density was 1.2, which was good, but 8. In the image of the time-based blank rotation, the density was decreased (0,6) and fogging occurred. The amount of triboelectric charge of the developer increased to +17.5 gC/g, and thin stripe-like fusion occurred on the developing sleeve "2". When the surface of this developer was observed using an electron microscope, some peeling of the shell was observed.

Comparative Example 2 Using core particles to which silica is not attached to the core material of Example 1, M n = 24130, M w 7M n =
A toner was obtained by encapsulating a strong electric composite of styrene-dimethylaminoethyl methacrylate (molar ratio 90/10) having a value of 1.92 in the same manner as in Example 1, silica was externally added to the capsule toner, and a developer was prepared. I got it.

Since a resin with a high molecular weight and a narrow molecular weight distribution was used, phase separation was not performed well, and the outer shell surface of this capsule I/ner had many protrusions, and at the same time, MIIIiI products of the shell were also observed. Observation using a transmission electron microscope revealed that some parts of the shell were uneven in thickness. The amount of triboelectric charge of this developer is +7.0 g C/g.
When the same test as in Example 1 was conducted, the initial image showed similar fixing properties, but the image density was 0.90, and J
% dryness was low, and the image quality also suffered from blurring and fogging. The image after 8 hours of shell rotation has a density of (1,23)
The frictional charging chamber of the developer was also +9.5 C/g, but after being left for about 5 hours, the initial image quality deteriorated to m;. At this time, pickpocket-
Bu surface 1-! There was no staining or fusion, and no peeling of the outer shell occurred.

Example 2 Calju/hewax 10 parts polyethylene wax 20 parts paraffin wax
70 parts magnetic material 8
IK obtained by melting and kneading the 0 part composition at 1.000C.
g of silica (Aerosil #30) in a molten state at 120°C.
0) Suspend 70g in 20M water at 95°C and mix with Ajihomixer (!l-1i' manufactured by Shukikachogyo) 9
Granulate at 000 r, p, m and tII particles of 5-20 l.
is. After filtering and drying the particles, use a hexyl mixer 10B.
Using the above particles J, OO, tl+; per jj part,
Silica (Nibsil E manufactured by Ichiki Shiri TJ) 2.0-;
(:, iJ part was added and stirred for 1 minute with dial 6 [1 setting) to adhere silica to the surface of the core material particles.

1 kg of the core material particles was mixed with slalene-dimethylamino-1-methyl methacrylate (monomer Φ, i%1 ratio 90:1).
0(7) Strong Φ, coalescence, number = p-equal molecule! ;Mn =6.7
85, Mw/Mn=5.65) in 2.5% DMF (
Styrene-dimethylaminoethyl methacrylate was added to the surface of the core material by dropping water into the solution 4 (dimethylformamide) for 60 minutes at a speed of 7 minutes per 25 m.
A capsule toner was obtained by precipitating 1.7.

100 tons of the obtained capsule toner, 1 part, 11 parts, silica (+', lI not Aerosil! JRP-130) 0.
A portion of 6Φ was added using a Henschel mixer to obtain a developer.

When this developer was used for image reproduction with P(, -30 (Canon copier)), an image of J☆I quality with an image density of lap 1.5 and no scattering was obtained, and an image of 400
No difference in image quality was observed before and after the 0-sheet durability. Also 4
The surface of the drum was observed after 1,000 sheets had been printed, and no fused toner was observed.

Comparative Example 3 Styrene-dimethylaminoethyl methacrylate of Example 2 (M n =about 5200.MW/Mn-about 1.
Capsule I was prepared in the same manner as in Example 2 except that 9) was used.
・When I obtained the developer and prepared the developer and used a PC and 30 machines, the initial image density was 1.3, but by the time 3,000 sheets had been printed, the image density had dropped to 1.0 and the driver J・on top 1
It was found that there was a tendency for toner filming development to occur.

Claims (3)

[Claims] (1) A capsule toner consisting of a core particle and an outer shell material covering the same, and having inorganic fine particles near the surface of the core particle, the main component of the outer shell being a vinyl polymer, and the weight average Molecular weight (Mw) and number average molecular weight (Mn)
A capsule toner having a ratio (Mw/Mn) of 3.5 or more. (2) The vinyl polymer contains a styrene monomer,
The capsule toner according to claim 1, which is a copolymer with a vinyl monomer containing a tertiary amino group. (3) Claim 1 having an outer shell formed by a phase separation method from an organic solution phase in which the outer shell material is dissolved.
Capsule toner described in section.