JPS5926743A - Electrophotographic liquid developer - Google Patents

Abstract

PURPOSE:To obtain the entitled developer enhanced in image developing density, superior in halftone reproductivity, and capable of developing with highly uniform density in large area parts, by dispersing toner particles having two specified peaks of particle diameter distribution. CONSTITUTION:The particle diameter distribution of toner particles has its peaks in the range of 0.01-1mum and 1-30mum in an electrophotographic liquid developer prepd. by dispersing the toner particles into a highly insulating and low dielectric constant aliphatic hydrocarbon or halogenated hydrocarbon solvent, such as kerosene, n-hexane, carbon tetrachloride, or perfluoroethylene. As a result, density of a developed image can be extremely elevated, halftone reproductivity can be enhanced, and density high in uniformity even in a large area image can be obtained by development.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a
, relating to a liquid developer for use.

Liquid developers are well known as developers for developing electrostatic latent images formed by electrophotography, electrostatic printing, recording, or electrostatic printing. This liquid developer has high insulation properties,
The carrier liquid is an aliphatic hydrocarbon and/or halogenated hydrocarbon having a low dielectric constant, and fine toner particles containing a colorant and a resin as main components are dispersed in the carrier liquid.

Toner particles of liquid developers that have been commonly used in the past have an average particle size of 114 m or less, and have a single peak-shaped particle size distribution. This is based on the knowledge that the smaller the toner particle size, the higher the wf corrosive force of the image.

However, with the average particle size and particle size distribution described above, there is a limit to the density of the developed image.

An object of the present invention is to develop a liquid developer for electrostatic photography that can dramatically increase the density of developed images, has excellent halftone reproducibility, and can be developed with highly uniform density even in large area image areas. It is located in a place that provides medicine.

That is, the present invention provides an electrostatographic liquid developer comprising toner particles dispersed in a highly insulating and low dielectric constant aliphatic hydrocarbon and/or halogenated hydrocarbon liquid, wherein the particle size of the toner particles is Particle size distribution ranges from 0.01 to 1 μm and from 1 to 30 μm
It is characterized by having a particle size distribution peak in the range of m.

The toner migration speed is expressed by the following formula μ2η μ: Toner migration speed (cV/Sec/V/crn)
q8: Toner blush 11I, loading density (μa/cd) r
o: ) Particle size of the toner (μ+I η: viscosity of the f8 medium (op's)) It can be said that it is larger than the particle size of the toner and the surface charge density of the toner.The toner according to the present invention The particles have an average particle size of 0.01~111rn and 1~30μ.
It has two particle size distribution peaks that are a mixture of 1 and 2, and because the small particle size toner is partially adsorbed on the surface of the large particle size toner, the migration speed of the toner increases due to the particle size dependence of the cutting allowance. It is thought that this will improve the performance efficiency.

However, if the large particle size toner is more than 50 wt %, the toner will have a large sedimentation property, and the charge control by the small particle size toner will be insufficient, resulting in a decrease in image density. If it is less than 1 wt%, ro is too small and the toner migration speed becomes low, resulting in poor i+li image density and uniformity.

Further, the specific gravity of the large particle diameter toner is preferably 0.5 to 1.4.

In order to obtain the J toner of the present invention, a small particle size toner and a large particle size toner each containing a >12 coloring agent and a binder resin as main components may be prepared and mixed.

The binding resin may be, for example, a petroleum aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon solvent having the general formula % [where R is hydrogen or a methyl group, A is -C00Cnli2n-H, or -0COCnllll]
n++ (the bulge is an integer from 6 to 2o). ] monomer (hereinafter referred to as monomer A)) and divinylbenzene or its alkyl (carbon number 1 to 20)
2t contains a copolymer obtained by polymerizing U4 form (hereinafter referred to as monomer B).

To make this copolymer, use the monomer A mentioned above, TOMOTSUMA-B.
M2A may be carried out in a petroleum-based aliphatic hydrocarbon or halogenated aliphatic hydrocarbon solvent in the presence of a polymerization initiator such as benzoyl peroxide or azobisindutyronitrile. Through this reaction, a copolymer having a three-dimensional structure in which the peripheral components of monomer A and monomers to B are crosslinked to each other in a network-like manner is obtained. Furthermore, monomer B used in this reaction has the property that it is solvated with the solvent before the j3j reaction, but is not solvated after the 11 reaction.On the other hand, monomer A has the property that it is solvated with the solvent before the
It has the property of forming a solvent phase with the solvent both before and after the j1ξ combination. Therefore, the resulting copolymer has the monomer B component as the center in the solvent, and the monomer Δ component solvated with the solvent is dispersed around it in a bonded state. Here common j1
During coalescence, the monomer Δ component contributes to toner dispersion stability (and thus maintenance of stability) and adhesion 1 (direction of 1). Note that the ratio of monomer B to monomer 8 is (1,
Os −1: t (2I(hi: ) approximately) is appropriate.

In addition, these monomer A and monomer B components contain other JI
A monomer L (hereinafter referred to as monomer C) can be added as appropriate.

To make a liquid developer using the copolymer thus obtained, generally 1 part by weight of the colorant is mixed with 0.3 to 3 parts by weight of the copolymer, and this is mixed with petroleum-based aliphatic hydrocarbon or halogenated Attritor in the presence of 10 to 20 parts of aliphatic hydrocarbon bath medium, d? - Disperse thoroughly using a dispersing machine such as Lumil or Redimir (concentrate it, then dilute it 5 to 10 times with a similar solvent. In this case,
(The copolymer dispersion prepared as described above can be used as it is for the copolymer and solvent. Also, if necessary when producing concentrated toner, It is also possible to add polarity control agents such as other trees other than coalescence.
The developer obtained in this way has a low viscosity, so it is easy to handle, and the low viscosity of this toner means that it has a 4i! j It has the advantage of making it easier to replenish the 4 precepts, and also causing gelation, assimilation, etc. during storage and causing separation.

Specific examples of the nr2 monomer include lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodenyl acrylate, hexyl methacrylate, hexyl acrylate, octyl. Examples include methacrylate, octyl methacrylate, cetyl methacrylate, cetyl acrylate, vinyl laurate, and vinyl stearate.

Examples of monomer B include 0-divinylbenzene, nl-
Divinylbenzene, p-divinylbenzene, p-methyldivinylbenzene, 0-ethyldivinylbenzene, p~
Butyldivinylbenzene, m-heny\-sildivinylbenzene, 0-nonyldivinylbenzene, p-f sildivinylbenzene, 0-undecyldivinylbenzene, p
-Stearyldivinylbenzene, O-methyldivinylbenzene, 0-ethyldivinylbenzene, p-hexyldivinylbenzene, p-nonyldivinylbenzene, rn
-tecyldivinylbenzene, p-undecyldivinylbenzene, 0-steer IJ divinylbenzene, and the like.

Examples of 7-mer-C include styrene, vinyltoluene, vinyl acetate, alkyl (1 to 5 carbon atoms) esters of acrylic acid or methacrylic acid (e.g. methyl methacrylate, ethyl acrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate). )), polyhydric alcohol di(meth)acrylates (e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate)
1., diethylene glycol diacrylate, diethylene glycol methacrylate V-), triethylene glycol triacrylate, triethylene glycol triacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6-hexane di-diacrylate, 1,6 -hexanethiol dimethacrylate, trimethylolproprozone trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane Tetraacrylate, tetramethylolmethanetetramethacrylate,
Dipropylene glycol diacrylate, diethylene glycol diacrylate, trimethylolhexane triacrylate, trimethylolethane triacrylate, penquerytrit detraacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol diacrylate Examples include recall dimethacrylate, trimethylolethane triacrylate, trimethyl 1''-lethane methacrylate, and the like.

As the polymerization initiator, benzoyl peroxide, t-butyl perbenzoate, diamyl peroxide, di-t-butyl, e-oxide, lauryl peroxide, azobisisozotyronitrile, etc. can be used.

"C" as a solvent is a petroleum-based aliphatic hydrocarbon or a non-logenated aliphatic hydrocarbon, such as kerosene, ligroin, n-hexane, n-hebutane, n-octane, i-octane,
i-Dodecane (commercially available products include Exxon's Iso, e-1 (GHL+: Naphza Black 6; Tsurpez 100 fathoms), carbon tetrachloride, monofluoroethylene, etc. A small amount of an aromatic solvent such as toluene or xylene can also be added to the aliphatic solvent.

Also, wax with a softening point of 60 to 130°C or H? Specific examples of commercial products of lyolefin are as follows.

Union Carbide (USA) DYNI
102DYNF 1 02 DYNH102 DYNJ 1 (12 DYNK 1 02 Monzanto (US) 01E LIZON 805 116z 705
A, 16 Sensando (US) 0RLIZON 50 126 Phillips (US) MARLEL 1005 92 Dupont (US) ALATHON -31031096 1284 1480 1695 2086 2284 2596 Allied Chemical (US) AC-71? Liebsen 1
702 98N 6&-6A 102 N 615 105 Sanyo Chemical J Bo Sunwax 131-p
108// 151-p 107w161
-pill tt 165-p 107N 17
1-p 105 N E-2095 Manufacturer Product Name Softening Point (℃) Genuine Chemical Paraffin Socks 60-9
8 Kobayashi Chemical Exposed Beeswax 65 Cetanol
80 Nagai Kako Exposed Beeswax 65 Iron Chemical Frozen 110 Coloring agent, caryl? black, oil sol,
Alkali blue, Fuclocyanine sol, Phthalocyanine green, Spirit black, Aniline black,
Examples include dyes or pigments such as oil violet, benzidine yellow, methyl orange, sylylia/tocarmine, fast red, and crystal violet.

As a polarity control agent, -C is a common one such as metallic phosphorus, lecithin, linseed oil, higher fatty acid, etc.

For small particle size toners, conventional liquid toners (Ricoh Type 1000, Ricoh Type 17010) are used.

Ricoh BS) toner, Ricoh M1-P toner, etc.) may be used as they are.

In addition, as large particle size toner, Fe, Ni, Cu
, Fe10B.

Although residual drops of 5i02, ZnO, Tl0I, etc., or the metal compound itself may be used, it is preferable that a substance such as a polymeric substance or the like that can be fixed by pressure is included. For example, organic or inorganic dyes and pigments can be used with resins (vinyl chloride, styrene resin, acrylic (θ(
fat, phenolic resin, rosin-modified maleic acid (☆(fat,
01 to 1 μm in which dyes and pigments are coated with resin are uniformly dispersed in petroleum resins, resins, etc.
O) Granules formed by agglomerating fine particles, pigment aggregates, or capsules 11η formed by wrapping the granules with a wall resin are used. Further, a hollow fine particle borer may be used so that the specific gravity can be adjusted by +1.

In addition, commercially available crow balloons, shirasu balloons, activated carbon particles, and toner for dry copying machines can be used. Note that when fixed on a recording sheet by a heated roller, it is better to use a material that can easily break large particle size toner into fine particles, since the image will not be bogged down and a good image will be obtained. It is preferable to use a capsule or a one-piece structure.

Below, production examples and examples of I0 (fat dispersion (containing the above copolymer)) are shown.

Manufacturing example 1 2, equipped with a stirrer, temperature H1 and reflux condenser.

Add 300 g of isooctane to the fourth flask of Δ. iil was taken and heated to 95°C. In this, dodecyl methacrylate/
-) 19 QIi, A solution consisting of 10 g of o-butyldivinylbenzene and azobisisobutyronitrile 6, ji' was added dropwise over 3 hours, and then heated and stirred at the above temperature for an additional 4 hours to perform the jIK synthesis reaction. , polymerization rate 94
4ff with viscosity 280cp and particle size 01-0.20μ at 8%
A fat dispersion liquid was obtained.

Production Example 2 300 J/ml of the resin dispersion prepared in Production Example 1 was mixed with 10/ml of colloidal silica in a flask, heated at 100°C for 3 hours, and then cooled to give a viscosity of 318 cps and a particle size of 03.
A resin separation solution containing colloidal silica of ~0.4 μm was obtained.

Production Example 3 Indodecane 3002 was placed in the same flask as in Production Example 1 and heated to 90°C. Next, a bath solution consisting of 2-uryl methacrylate-1.3o0&, p-divinylbenzene 25&, and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, and the mixture was heated and stirred at 95°C for 4 hours.
A polymerization reaction was carried out, with a polymerization rate of 96.5% and a viscosity of 380 cp.
A 4+1 fat dispersion with a particle size of 01 to 03 μm was obtained.

Production Example 4 300 g of the IJ liquid obtained in Production Example 3 was mixed with bleached beeswax 20.9 in a flask, extruded at 90°C for 2 hours at 4N, and cooled to obtain a viscosity of 215 cp.

Ten resin dispersions with a particle size of o and i to 1.0 μm were prepared.

Production Example 5 In the same flask as in Production Example 1, 300 g of -G and 30.9 g of colloidal silica were placed in the same flask as in Production Example 1, and heated to 90°C. In this, 2-ethylhexylmethac')V-)xs
og, p-divinylbenzene 20 & lauroyl peroxide 639 were stirred at the above temperature for 4 hours to carry out a nail platform reaction, and a resin dispersion with a polymerization rate of 98.296, a viscosity of 126 op, and a particle size of 0.1 to 30 μm was prepared. (It was.

Production Example 6 In the same flask as Production Example 1, 300 g of Isopar was heated to 990'C.

Nanatsuma, vinyl toluene 3Q, 9. Inzotyl methacrylate 20g, styrene 10JI+.

Methacryl tt'(3&), diethylaminoethyl methacrylate 2I, and 5:9 of azobisisobutyronitrile were mixed in a flask and reacted at 90°C for 5 hours.

Example 1 Horn-7” black (M-1 manufactured by Mitsubishi Car Y+?
1) In lii' production example 1? 47 resin dispersion 5oI kerosene
100. p Dry toner Ricoh type 6000 (specific gravity 1.14)
Disperse 15Jil in a kedimir for 6 hours until the viscosity is 20.
．． A liquid developer for electrostatography was prepared by dispersing 10 g of concentrated 1.07 IP toner in kerosene 11 to obtain a toner containing a mixture of toner particles with average column diameters of 0.28/1 m and 13.511 m. It was done.

Next Tonowa 1. 1 using a commercially available electrophotographic copying machine using an image agent.
Copying was carried out on 441;-t:, a photosensitive zinc oxide film, and a copy with an image density of 1.36 and an image constant M ratio of 87.2 inches was obtained.

For comparison, a developer prepared in the same manner except that the dry toner was not used at all had an image density of 1.2.
It was 6. 1. The image fixation rate was calculated from the formula (image density after 5 reciprocations) using a rubber tester.

Example 2 Carbon black (Columbia car yI?/Sei-made 2-
Ben 14) 15J? In Production Example 2, 100g kerosene
100/ Manganese naphthenate 1yBR-
89 (manufactured by Mitsubishi Rayon Co., Ltd., acrylic polymer particles (ratio j
lt1.10)) 10& was treated in the same manner as in Example 1 to prepare an electrostatic photographic liquid developer. Note that the viscosity of the concentrated toner is 18.2 cp,
Particles with average particle diameters of 05 μm and 201 Im were mixed.

Next, using this developer, copying was carried out in the same manner as in Example 1, and a copy was obtained with a 1iljif+R density of 1.41 and an image fixation rate of 86%.

All Bft ~ 89 (for those not used, rule f1j
! The concentration was 1.32.

Example 3 Calf 3? /Black (Sieben 5250 manufactured by Columbia Carbon) 15, ji'j obtained in Production Example 3,
tA fat dispersion 100. ! i1 kerosene
100I Lencan 3I was treated in the same manner as in '=A Example 1 to prepare a liquid developer. 20.9% of dry toner Ricoh Quizo 6000 was added to concentrated toner 2 (10.9%) and stirred in a stirrer to obtain a toner containing a mixture of particles with average particle diameters of 0.23 μm and 14 μm.Hereinafter, this developer After making a copy in the same manner as in Example 1 using the same method as in Example 1, it was subjected to a desensitizing treatment and used as an offset master for offset printing, resulting in a print life of 30,000 sheets. The image constant rate of offset master) was 89%.

Example 4 Benzidine Yer” ~ (Inu Nisseika Co., Ltd. N) 3
0/Produced in Production Example 4 (☆(Fat dispersion 7
0/Kerosine 1009 Canthenic Acid Dig #5. ! i'
Glass balloon (ratio gr10.80) 1
0, lit was treated in the same manner as in Example 1 to obtain a Cassie static.
A liquid developer for printing was prepared. The viscosity of the concentrated toner was 12.5 cp, and the average particle size was 08 μm and 281 μm.
It was a totuo with a 1m long wako mixed in.

Next, when I made a color copy using this glare f-area agent on r1-da Jli lead-sensitive Art using a commercially available color ILL child photo copying machine, I got a clear pIG color iI! A JJ image was formed.

Example 5 Car d? Blank (Mitsubishi Car +1? MA-11 made by Nensha)
) 209 Resin dispersion obtained in Production Example 5
130I kerosene 100g Shirasu balloon (specific gravity 0.93) 3 (1
was processed in the same manner as in Example 1, and the electrostatic photograph JIjrtffi
(4: SuL liquid was prepared. Viscosity of concentrated toner &12
5.5ap tear, average grain a0.1811m and 25μm
7J''-fl?, the toner was present.

Hereafter, using this developer, copies were made with the same quadruplets as in actual sister example 1, and the image magnetism was 1.44, iit + i image sil '3.
'2 rate 86. θ% copies were obtained.

Even if no Shirasu balloon was used (σ), the image density was 4'! , it was 1.30.

Example 6 Zero gin modified maleic acid resin 100y carmen black (manufactured by Mitsubishi Kasei Co., Ltd.) J +1? file =, i4)
The zoy was mixed in a heated roll mill, cooled and ground, and colored with an average grain size of about 20 μm (11 pieces of θ1 fat powder [1 + older brother]).

On the other hand, add the stirrer/temperature R1-reflux condenser to the Le 111 eco container.
) 3009 was taken and heated to 95°C. In this 2-
Ethylhexyl methacrylate)-2001, glycidyl methacrylate 10g, azo 1sisobutyronitrile 3
After adding 311g of the mixture dropwise at a constant rate, the mixture was stirred for 1 hour to further divide the anti-J6 into portions.
/ Add 1 g of diuryl dinotylamine and 90°
Anti-J for 20 hours in C? J j is the person who was affected by the above reaction.
I esterified the K combination. The degree of esterification and the decrease in acid value σ were in the range of 25 to 30%. next,
Add Isovar G500,9 to the S-Bul-Ihiha reaction solution and add methyl methacrylate 509 and azo 1-sisobutyronitrile 3y dropwise at a constant rate over 3 hours at 90°C. nil i own 111 now about 5 o'clock (110 ((with 461 flti
CB component] 17. Make 6 laps of latex liquid.

The above Δ component 14. V Above B
80. fl'1 Isopar/L/H15M small y1? -g' with an average particle size of 10 p after dispersion with Lumil for 24 hours! A shrunken toner was obtained. Separately, car] Jen black (Mitsubishi Casi car ln≠44)
10(1,)1'lilauryl mechcrylate
50y Isopar II l
00, p to 11? - Dispersion was carried out with Lumil for 14 hours to obtain a dark toner (11) with an average particle size of 0.25 μm. 100y of each of these toners was taken and
It was diluted with 1e to make a vll liquid.

This is commercially available 1 (L child photo copy [Ricoh jR2, ■] T
When the static latent image on the Sa photoreceptor was developed and transferred using the photoreceptor, its characteristics were as shown in Table 1.
As shown in [Especially, the image density is much higher (because there is less background staining and the transfer paper is 4.1% lA (solvent)
('j'i': The amount of f was small.

Further, this developer was placed in a beaker and left undisturbed for one week to allow the toner to settle, and then the precipitated toner was dispersed by 11 J° by simply shaking it lightly. After one week had elapsed, the developing solution was lightly stirred and used for copying, and the image characteristics were comparable to those in the early stages of printing.

Example 7 Unsaturated polyester (Kao Atlas Co., Ltd., Atrac 382A) 1
0(1)) -d? Black (Mitsubishi Color Car SR?
44) After kneading in an IA roll mill, the mixture was cooled and pulverized to obtain a colored resin powder (component) having a volume average particle size of about 771 m.

Meanwhile, in a container equipped with a stirrer (temperature reduction) and Ic cooler, add -II 300 and P to 95℃.
heated to. Into this, 200 g of 2-ethylhexyl methacrylate, 80 g of glycidyl meccumate, and 3 y of asopisisozothyronitrile were added dropwise at a constant rate over 3 hours to react, and the mixture was further stirred for about 1 hour to complete the reaction. This is methacrylic VTS
i.) 0.1 g of 1hydroginone and 1 g of diuryldimethylamine were added and reacted at 90°C for 15 hours to esterify the copolymer obtained in the reaction M. The degree of esterification was 20-30 as determined by market price. Next, add Isopar 11500 to the esterification reaction solution! Add i' and 95
At 6C, 50 g of methyl methacrylate and 3 g of azobisinzothyronitrile were added dropwise at a constant rate over 3 hours, and after maintaining the liquid temperature at a constant temperature for another 5 hours, it was cooled to form a latex (resin content: 17.5%). [Component B].Next, Isovar G300.9 was added to 300y of this dispersion, and then heated to 90°C to form a polyethylene wax [Component C]15
0y is added, heated and melted for 1 hour until it becomes transparent, stirred and dispersed, and then cooled (U-C dispersion).

In addition, after pulverizing the dithyl rubber (1) component], 20y of it was added to Isovar II 100,! iI and stirred for 24 hours to dissolve) 3゜Next, the above A component 15I above 13-
C dispersion liquid 40g above ingredients dissolved
50g Ainnotunol) I
I J, Og at small pole mill, 24
Time dispersion was performed to obtain a concentrated toner having an average particle size of 6.811 m. Separately, Karl Black (Pviog)
alA) 3090 Gin-modified Malein Dense 3 (1 Isopar H 100g was dispersed in a ball mill for 24 hours, and the average particle size was 0.13μ.
A concentrated toner was obtained.

Each of these toners was diluted from 60.9 to -621 to prepare a developer.

When this was used in a commercially available electrophotographic copying machine to develop and transfer an electrostatic latent image on a Se photoreceptor, its properties were excellent as shown in Table 1.

Further, the redispersibility of the toner in this developer was as good as in Example 1.

Example 8 A styrene-n-butyl methacrylate copolymer (mole ratio 7:3) was ground in a jet mill to obtain resin particles [component A] having a volume average particle diameter of about 7.5 μm.

On the other hand, (fL 1,6 equipped with stirrer, thermometer, reflux condenser)
-H300y was placed in a three-necked container and heated to 90°C. In addition, 80% peracasite P-171 was added to 2-ethylhexyl methacrylate 2009.
! IL solution) 9 degrees, and azopisinzotyronitrile 2
g was mixed. This mixture was dropwise polymerized in the container for 4 hours, and then for another 1 hour (W press, solid content 48.
A 3% resin [component B] dispersion was prepared. This molecule rk
Liquid 20. & and Calf Gen Black 59, polyethylene wax 2 og and Isopar II 100 & and 9
Disperse and mix while heating to 0°C [B-C dispersion]
.

Also, styrene sitadiene rubber (styrene 20molv)
After pulverizing [Ingredient D], 20. ! ? was placed in Iso-e-le H100.9 and allowed to melt for 24 hours.

Next, A component 13 IB-C 11 liquids 809 pieces 11
Is 509 a small H? - Dispersion was carried out in Lumil for 24 hours to obtain a shoe making toner having an average particle size of 20 μm.

This toner and Ricoh DT-1200) toner (average particle size 0
．． 3 μm) and 50.9 each, isobar) I
Dilute with 1 liter and develop? It was set as it. Example 6
When it was subjected to copying in the same manner as above, its properties were rated as good 7, as shown in Table 1.

Also, the first redispersion of this developer was carried out in step 1! /
! Like l 1, it is in good condition and has an A rating.

Embedded negative side 9 Lysine-modified phenol resin (manufactured by Ban Jl'M Kasei Co., Ltd., grade 13145G) was used in place of the unsaturated polynisdel J't1+ fat in Example 7, and A component resin JiQ average particle I. The same procedure as in Example 7 was carried out except that about 6.7 Jim was used, and the solid content was 1.5 inches. When diluted and used as a developing solution for copying, its properties were as follows.
As shown in 1, the results were good.

Further, the circular dispersion of the toner of this developed image I'lk was determined in Example 1.
It was also good.

Example: A procedure was carried out in the same manner as in Example 3, except that in place of the styrene-11-butyl meccrylate copolymer, an unsaturated, 1'' polyester resin (manufactured by Kako Atlas Co., Ltd., Atrac 382E) was used. ＃Rit・ner was obtained, and it was diluted with Isobal II so that the solid content was 1.5 grams. As shown in Table-1, it is in good condition (Jj)
Ivy.

Example 11 Polystyrene particles (average particle diameter 10 μm) and recoatner Taizo 1ooo (average particle diameter (+, 371 m) were each taken at 10y and diluted with 200g to prepare a developer. The characteristics of this developer are shown in Table-1. As shown in the figure, the results were good.

Example 12 One spherical activated carbon, charcoal (3r, average particle size 28 μm), and Recoatner Tyzo 1000 (average particle size 03 μm) were mixed into 10 &
The solution was diluted with 200.9% to obtain a developer. The properties of this current edge liquid were good as shown in Table 1.

(Left below) Example 13 Methyl methacrylate 500y Azobisisozothyronitrile 5y Nolone
30
0y1-' f sylbenzene sulfonic acid z-i, o
500 g of distilled water was stirred at high speed.

This dispersion was charged into a pressurized reaction vessel and polymerized at 60°C for 8 hours. ] [The hardware was thoroughly washed with distilled water, heated and dried at 50°C for 3 hours, and then further heated at 80°C for 30 minutes.
This 21 Solima particle 10 with a particle size distribution of 1311 m
9 and Ricoh wet toner Taizo 1ooo ioo, p, and Isopar G 10100O as a diluent were added to prepare a liquid developer. Toner particles with average particle diameters of 03 μm and 10 μm were mixed.

When this developer was copied using a commercially available wet copying machine DT-750, the image density was 144, the gradation was 10 steps, and the M image power was 9.
2 pieces/fight were obtained.

Styrene 2509 Acrylonitrile 250I Benzoyl peroxide 3yZoku7 300
9 Glycerin monooleate 10g steamed
500 g of water was stirred at high speed. This dispersion was charged into a pressurized reaction vessel at 60°
Polymerization was carried out at C for 8 hours. After washing the polymer thoroughly with distilled water,
After drying at ℃ for 3 hours, heating at 90℃ for 30 minutes resulted in a hollow particle size of 5 to 10μm with a ratio of 086+I! 'I got Rimmer particles. Add Ricoh wet toner Quip 1700 to this polymer particle 20 & 200F, Iso/"G 1
000 n1ll! added. Average particle size 0.26μ and 8
A toner mixed with μ toner particles was obtained.

When this developer was copied using a commercially available wet-type copying machine DT-180OR, an image humidity of 1.40.1 and 11 steps was obtained, and a resolution of 9.8 lines/frame was obtained.

Claims (1)

[Scope of Claims] 1. An electrostatographic liquid developer comprising toner particles dispersed in an aliphatic hydrocarbon and/or halogenated hydrocarbon liquid with high insulation properties and low dielectric constant. A liquid developer for electrostatic photography, characterized in that the particle size distribution of the particles has a particle size distribution peak in the range of 0.01 to 1 μm and in the range of 1 to 30 μm.