JPH03200268A - Liquid developer for electrostatic charge image - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

[Industrial Field 1] The present invention relates to a liquid developer for hot roll fixing used in electrophotography, electrostatic recording, electrostatic printing, etc. (Prior art) As a liquid developer for heat roll fixing rolls, JP-A-63
-301966 to 301969, 64-500
No. 62-50067, No. 64-52167, No. 64-
142560-142561, etc. Since these are carrier liquids mainly composed of aliphatic hydrocarbons, the aliphatic hydrocarbon gas is discharged outside the copying machine, and silicone oil must be supplied to apply to the fixing roll. There were problems such as the copying machine becoming more complicated and the number of consumables increasing.

[Objective 1 of the present invention] An object of the present invention is to reduce hydrocarbon solvent gas generated from copying machines. To make it possible to remove an oil application device to a fixing roll in a hot roll fixing device using a liquid developer, and to save the trouble of oil supply. By mixing in a certain proportion of nonflammable liquid, the risk of ignition is reduced. (Structure of the Invention) In recent years, hot roll fixing has been proposed as a fixing method for liquid developers that has high thermal efficiency and is capable of high-speed fixing. If a hydrocarbon solvent is used as the carrier liquid and this fixing method is adopted,
Although the amount of solvent gas emitted per unit number of sheets is slightly reduced compared to conventionally used atmosphere fixing, a large amount of solvent gas is generated when a large number of sheets are copied at high speed. Also,
It was necessary to apply silicone oil to improve the releasability between the toner layer and the fixing roll. The present invention aims to improve the above-mentioned drawbacks, increase the cohesive force of the toner, and prevent so-called ``hot offset'' by incorporating a fluorine-based solvent as a carrier liquid. Fluorinated solvents used in the present invention include Fluorinert FC-77, FC-40, FC-43, FC-70
(manufactured by Kahei 3M), Afrud, E-10, E-1
6, E-18 (Asahi Glass f!A), and the like. In addition, examples of silicone-based solvents that may be used at the same time include KF96 (Shin-Etsu Silicon), 5H200, 5H3
44 (Toshiba Silicon), TSF451 (Toshiba Silicon), etc. In addition, decamethyltetrasiloxane, octamethyltrisiloxane, etc. may be used. In addition, cyclohexane, n-
hexane, n-hebutane, n-octane, n-nonane,
Petroleum hydrocarbons such as isooctane, isododecane, ligroin, and mixtures thereof (commercially available products include Isopar E, G, H, L, and V manufactured by Exxon Chemical Co., Ltd., and Shellsol 71 and Solubbesso 150 manufactured by Shell Oil Co., Ltd.) ), and these may be mixed and used as appropriate. To reduce the amount of transfer agent, use a carrier liquid! It is preferably 0 cst or less, preferably 3 cst or less. In the present invention, as a means for increasing the cohesive force of toner,
Examples include using a self-crosslinking polymer and a crosslinked high molecular weight polymer in the toner resin component. The self-crosslinking polymer used in the present invention is preferably a copolymer or modified product containing a diene compound having a conjugated double bond. For example, compounds with vinyl groups and conjugated double bonds, such as styrene-butadiene copolymer, styrene-chloroprene copolymer, styrene-isoprene copolymer, styrene-piperylene copolymer, acrylonitrile-butadiene copolymer, etc. Particularly preferred are copolymers with diene compounds. Yet another feature of the present invention is that the self-crosslinking type polymer described above is used in combination with a high molecular weight polymer that is already crosslinked without self-crosslinking. Already crosslinked polymers that can be used in the present invention include aromatic vinyl compounds such as styrene, esters of unsaturated aliphatic monocarboxylic acids such as acrylic esters, or esters of unsaturated aliphatic monocarboxylic acids such as maleic esters. Homopolymer copolymers of esters of unsaturated aliphatic polycarboxylic acids, high molecular polymers made by crosslinking terpolymers with compounds having polyfunctionality of dihydric or higher valence, or dihydric alcohols and dibasic acids and trihydric acids. Non-linear polyester resins made of the above alcohols or carboxylic acids are preferred. Generally, a polymer having a weight average molecular weight/number average molecular weight of more than 40 and a weight average molecular weight of too, 000 or more is preferable. Moreover, self-crosslinking type coalescence/crosslinking type coalescence is 0.
5/9.5 to 715 is preferred. As a coloring material that can be used in the present invention, Printex V
, Printex U, Printex G, Special Black 15, Special Black 4, Special Black 4-B (manufactured by Degussa), Mitsubishi #44, #30, M
R-11, MA-100 (manufactured by Mitsubishi Kasei Corporation), Raven 1035, Sieben 1252. New Spect N (manufactured by Columbia Carbon), Regal 400.660
, Black Burl 900.1100.1300, Mogul Shikori (manufactured by Cabot), and inorganic pigments such as phthalocyanine blue, phthalocyanine green, sky blue, rhodamine lake, malachite green lake,
Methyl violet lake, peacock blue lake,
Naphthol Green B, Naphthol Green Y, Naphthol Yellow S, Naphthol Red, Lysol Fast Yellow 2G, Permanent Red 4R, Brilliant First Scarlet, Hansa Yellow, Benzidine Yellow, Lysol Red, Lake Red C, Lake Red D, Brilliant Carmine 6B, - Organic pigments such as Manent Red F5R, Pigment Scarlet 3B Indigo, Thioindigo Oil Pink and Bordeaux 10B. The pigment can be treated by mixing and crushing the above pigment with the resin using a two-roll machine, a kneader flasher, or the like. Further, the following resins may be used together with the above resins. Eastman Chemical
al) manufactured by (N-10, N-11, N-12, N-14
, N-34, N-45, C-10, C-13°C-15
, C-16, E-10, E-11, E-12, E-14
, E-15) Manufactured by Kochu Petrochemical Co., Ltd. (110P, 220P, 220MP, 820MP, 41
0MP, 210MP, 310MP. 405MP, 200P, 4202E, 4053E) Manufactured by Kochu Kasei (131P, +5IP, 16IP, 17IP,
E300. E250P) manufactured by Sasol (formerly, H2, AI, A2.A3.A4) BASF (BAS
Manufactured by F) (OA WAX, A WAX) Manufactured by Petrolite (Petrol 1te) (Valeco (
BARECO) 500. Same 2000. E-730,E
-2018, E-2020, E-1040, Petronaba C, Petronaba C-36゜C-400
, C-7500) Manufactured by Hoechst (PE580. PE130. PED121. PE
D136. PED153. PED521, PE
D522. PED534) Manufactured by Union Carbide (DYNI, DYNF, DYNH, DYNJ, D
YNK) Monsando (ORUZON) 805,705.50) DuPont (^LATHON) 3.10.12. +4
．． 16.20.22.23) Allied Chemical Company (AC Polyethylene 6.6A, 615) Kou Polychemical Company (Evaflex 150.210.220.250.2
60.310.360°410.420,450,46
Synthetic polyesters such as 0,550,560), polypropylene and modified products thereof, natural waxes such as carnauba wax, montan wax, candelilla wax, shoukane wax, oculie wax, rice bran wax, wood wax, ester gum, Natural resins such as hardened rosin, natural resin-modified maleic acid resins, natural resin-modified phenol resins, natural resin-modified polyester resins, natural resin-modified pentaerythtol resins, and natural resin-modified hardened resins such as epoxy resins can be used in combination. Further, as the dispersing resin preferably used in combination in the present invention, the vinyl monomer A having the general formula % (R, represents H or CH, and n represents an integer from 6 to 20) and the general formula Vinyl monomers represented by the formula %) and vinylpyridine, vinylpyrrolidone, ethylene glycol dimethacrylate,
Examples include copolymers and graft copolymers of each type of monomer B selected from styrene, divinylbenzene, and vinyltoluene, or several types of monomers. In addition, when using a silicone solvent as a supporting liquid, a silicone material having an acroyl group,
L34080 manufactured by Shin-Etsu Silicon Co., Ltd. may be copolymerized, and similarly L34080 manufactured by Toagosei Kagaku Co., Ltd., TMO701, FMO711, FMO721, FM manufactured by Chisso Corporation may be copolymerized.
O725 may also be used. By putting these coloring materials, resins, and carrier liquid into a dispersing machine such as a ball mill, kitty mill, disk mill, or bottle mill, dispersing and mixing them, a concentrated toner is prepared, and this is dispersed in the carrier liquid of the present invention. A developer can be obtained. [Example] In the following examples, all "parts" represent "parts by weight." Formulation Example 1 Formulation Example 2 Formulation Example 3 Example 1 Resin of Formulation Example 1 70 parts Carbon black (Pr1ntex V manufactured by Degussa) 3
0g11 was mixed with two rolls at 90°C for 30 minutes and then ground. 50 parts of the above-mentioned pulverized material Isopar H (trade name of EXXSON) 20
After dispersing for 24 hours, 300 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated toner. Take 200g of this and use Florinat FC.
It was diluted in a mixed solvent lQ of 50% -72 (manufactured by Kahei 3M Co., Ltd.) and 50% KF96 (manufactured by Shin-Etsu Silicone Co., Ltd., viscosity 3 cst) to prepare a developer. Example 2 Resin of Formulation Example 2 57 parts 250
8 parts of P (polyethylene made by Kochu Kasei Co., Ltd.) and 35 parts of A60 (carbon black made by Mitsubishi Kasei Co., Ltd.) were mixed with a flasher and then pulverized. 60 parts of the pulverized product, 200 parts of a 10% solution of the copolymer, and 100 parts of Isopar H were placed in a ball mill and dispersed for 24 hours, and then 300 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated toner. Take 200g of this and use Fluorinert FC-72.
It was diluted in a mixed solvent IQ of 50% (manufactured by Kahei 3M) and 50% Isopar H to prepare a developer. Example 3 0.2 parts of Naimeen 3202. The result was just like the robe. AC400A (manufactured by Allied Chemical Co.) 10 parts Lisgal 400 (Cabot Company) 30 parts at 140°C, 60
The mixture was mixed and pulverized with a flasher for a minute. A developer was prepared in the same manner as in Example 1. Comparative Example Comparative developers 1 to 3 were obtained in the same manner as in Examples 1 to 3, except that Isopar H was used as the diluent. An oil-less fixing test was carried out using a test machine in which the fixing section of Lif-type CT5085 was improved to a heated roll fixer. It can be seen that a medium temperature was obtained, and hot roller fixing was possible. Continuous copying was carried out using a test copying machine in a closed room, and the solvent gas concentration was measured. When using the comparative developer, the concentration of solvent gas was 300 to 360 ppm, whereas with the developer of the present invention, it was 80 to 360 ppm. It was halved to +50pp+n. (Effects 1) By using the developer of the present invention, hot roll fixing is possible without applying oil to the fixing roll and without causing an offset phenomenon. The amount of hydrocarbon gas generated by copying machines has also been reduced.

Claims (1)

[Claims] An electrostatic photograph in which toner particles made of a colorant and resin are dispersed in a carrier liquid of high resistance and low dielectric constant made of a liquid mixture of a fluorine-based solvent, an aliphatic hydrocarbon solvent, and/or a silicone-based solvent. A liquid developer for electrostatic images, characterized in that the resin component contains a self-crosslinking polymer and a crosslinked polymer.