JP2936516B2 - Liquid developer for electrostatic image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial fields]

The present invention relates to a hot roll fixing liquid developer used for electrophotography, electrostatic recording, electrostatic printing, and the like.

[Prior art]

As a liquid developer for heat roll fixing roll,
Nos. 301966 to 301969 and 64-50062 to 50067 and 64
-52167 and 64-142560 to 142561.
Since these are carrier liquids mainly composed of aliphatic hydrocarbons, the oil of the aliphatic hydrocarbons is discharged out of the copying machine, and silicone oil must be supplied for application to a fixing roll. There have been problems such as a complicated copying machine and an increase in the number of consumables.

[Object of the present invention]

An object of the present invention is to reduce a hydrocarbon solvent gas generated from a copying machine. In a hot roll fixing device using a liquid developer, an oil applying device can be removed from the fixing roll, and the trouble of oil supply can be eliminated. By mixing incombustible liquids at a certain ratio, danger such as ignition is reduced.

Configuration of the Invention

In recent years, a hot roll fixing method has been proposed as a fixing method of a liquid developer having high thermal efficiency and capable of high-speed fixing. If a hydrocarbon solvent is used as the carrier liquid and this fixing method is adopted, the amount of solvent gas emitted per unit number will slightly decrease compared to the conventionally used atmosphere fixing method, but it will be possible to copy many sheets at high speed. When this occurs, a large amount of solvent gas is generated. Further, in order to increase the releasability between the toner layer and the fixing roll, it was necessary to apply silicone oil. An object of the present invention is to improve the above-mentioned drawbacks by adding a fluorine-based solvent as a carrier liquid, increase the cohesive force of the toner, and prevent so-called "hot offset". Fluorinated solvents used in the present invention include Fluorinert FC-77, FC-40, FC-43, FC-70 (all manufactured by Sumitomo 3M), Aflud, E-10, E-16 and E-18. (Hereinafter, manufactured by Asahi Glass Co., Ltd.). Silicone solvents that may be used at the same time include KF96 (Shin-Etsu Silicon), SH200, SH344 (Toray Silicon), TSF451 (Toshiba Silicon), and other decamethyltetrasiloxane, octamethyltrisiloxane, etc. May be used. Also, cyclohexane as an aliphatic hydrocarbon solution,
Petroleum hydrocarbons such as n-hexane, n-heptane, n-octane, n-nonane, isooctane, isododecane, ligroin, and mixtures thereof (as commercial products, Isopar E, G, H, L, K, manufactured by Exxon Chemical Co., Ltd.) V, Shell Sole 71, Solbesso 150, etc., manufactured by Shell Petroleum Co., Ltd.). In order to reduce the transfer solvent, the carrier liquid should be 10 cst or less, preferably 3 cSt or less. In the present invention, as a means for increasing the cohesive strength of the toner, use of a copolymer comprising a component composed of a monomer having an active halogen atom and a component composed of an acrylic monomer can be mentioned. The proportion of the monomer having an active halogen atom in the copolymer is about 0.5 to 10% by weight, preferably about 2 to 5% by weight. The monomer having an active halogen atom is, for example, one represented by the following general formula (1) or (2). In the formula, Y ₁ is an oxy group, an alkyleneoxy group, a phenyleneoxy group, an oxyphenylene group, an oxyalkylene group, a carbonyloxy group, an oxycarbonyl group, a carbamide group, a phenylene group, or (Where Y ₃ represents an alkylene group or a substituted alkylene group), Y ₂ represents an alkoxy group, an acyl group, a phenyl group, or a phenyloxy group, and A represents a vinyl group, an alkyl-substituted vinyl group, or an allyl group. represents a radical, R represents a hydrogen atom or a methyl group, X represents a halogen atom, a-Y ₁ group and Y ₂ groups has a substituent constant of -0.1 greater Hammett. Preferred specific examples of such a monomer include the following. Specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate,
Isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenylene acrylate, methyl α-chloroacrylate, etc. Acrylic esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate
Examples include methacrylates such as octyl, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. be able to. Further, preferred examples of the monomer that can be copolymerized with the above monomers include a styrene monomer, and specific examples thereof include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-
Methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene,
3,4-dichlorostyrene and others can be mentioned. It is preferable to include a cross-linking agent containing two or more functional groups that react with an active site generated by elimination of an active halogen atom of the active ingredient. Active polyamines are useful as the crosslinking agent. Preferred crosslinking agents include, for example, a composition of hexamethylenediamine carbamate and dibasic lead phosphite, a composition of hexamethylenetetramine, a composition of sulfur and triethyltrimethylenetriamine,
A composition of mercaptoimidazole and lead red, ammonium benzoate, a composition of fatty acid metal salt and sulfur, and the like can be used. By including such a cross-linking agent, the toner material in the developing cleaning member of the copying machine is positively made to have a high molecular weight, and therefore, it is possible to reliably prevent the development of the back surface stain. Colorants that can be used in the present invention include Printex V, Printex U, Printex G, Special Black 15, Special Black 4, Special Black 4-B (hereinafter Degussa), Mitsubishi # 44, # 30, MR -1
1, MA-100 (Mitsubishi Kasei), Raven 1035, Raven 1252, Newspect II (Columbia Carbon), Legal 400, 660, Black Pearl 900, 110
Inorganic pigments such as 0, 1300, Mogar L (from Cabot) and phthalocyanine blue, phthalocyanine green, sky blue, rhodamine lake, malachite green lake, methyl violet lake, peacock blue lake, naphthol green B, naphthol green Y, naphthol green Yellow S, naphthol red,
Lisor First Yellow 2G, Permanent Red 4
Organic pigments such as R, Brilliant First Scarlet, Hansa Yellow, Benzidine Yellow, Lisor Red, Lake Red C, Lake Red D, Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B Indigo, Thioindigo Oil Pink and Bordeaux 10B. . The pigment can be processed by kneading and pulverizing the above pigment with the resin by using a two-roll mill, a kneader flasher or the like. Further, the following resin may be used together with the above resin. Eastman Chemical (N-10, N-11, N-12, N-14, N-34, N-45, C-10, C-1
3, C-15, C-16, E-10, E-11, E-12, E-14, E-15) manufactured by Mitsui Petrochemical Co., Ltd. (110P, 220P, 220MP, 820MP, 410MP, 210MP, 310MP, 405MP, 20
0P, 4202E, 4053E) Sanyo Chemical (131P, 151P, 161P, 171P, E300, E250P) Sasol (H1, H2, A1, A2, A3, A4) BASF (OA WAX, A WAX) manufactured by Petrolite (BARECO 500, 2000, E-730, E-2018, E-202
0, E-1040, Petronaba C, C-36, C-
400, same C-7500) Hoechst (PE580, PE130, PED121, PED136, PED153, PED521, PED522, P
ED534) manufactured by Union Carbide (DYNI, DYNF, DYNH, DYNI, DYNK) Monsanto (ORUZON 805,705,50) Dupont (ALATHON 3,10,12,14,16,20,22,23) Allied Chemical Company (AC polyethylene 6,6A, 615) Mitsui Polychemical Company (Evaflex 150,210,220,250,260,310,360,410,42
0,450,460,550,560) Synthetic polyesters such as polypropylene, modified polyesters thereof, carnauba wax, montan wax, candelilla wax, sugar cane wax, oculy wax, beeswax, wood wax, natural wax such as wax, ester gum, hardened rosin, etc. Natural resin, natural resin modified maleic resin, natural resin modified phenolic resin,
A modified natural resin such as a modified natural resin polyester resin, a modified natural resin pentaerythritol resin, or an epoxy resin can be used in combination. The dispersing resin preferably used in combination in the present invention includes (R ₁ represents H or CH ₃ , n represents an integer of 6 to 20) and a vinyl monomer A represented by the following formula: (R ₁ is H or CH ₃ , R ₂ is H, C _n H _{2n + 1} [n = 1-5], C ₂ H ₄ OH, [M = 1 to 4]. A) a vinyl monomer represented by the formula: vinyl pyridine, vinyl pyrrolidone, ethylene glycol dimethacrylate,
Each of the monomers B selected from styrene, divinylbenzene, and vinyltoluene may be used alone, or several types of copolymers and graft copolymers may be used. When a silicon solvent is contained as a carrier liquid, a silicon material having an acryloyl group to improve dispersibility, LS4080 manufactured by Shin-Etsu Silicon, or the like may be copolymerized, and similarly manufactured by Toa Gosei Chemical Co., Ltd. AK-5, and TM0701, FM0711, FM0721, and FM0725 manufactured by Chisso Corporation may be used. Put these coloring materials, resin and carrier liquid into dispersing machines such as ball mill, kitty mill, disk mill, pin mill, etc.
Dispersion and kneading are performed to prepare a concentrated toner, which is dispersed in the carrier liquid of the present invention to obtain a developer.

EXAMPLES In the following examples, "parts" all mean "parts by weight". Production Example 1 50 g of ethyl acrylate and 4 of methyl methacrylate
6g and glycidyl methacrylate monochloroacetic acid adduct
4 g and sodium alkylbenzene sulfonate 3 g, sodium bisulfite 0.03 g, potassium thiosulfate 0.5 g, sodium borate 1 g, and water 250 g were mixed at a temperature of 50 ° C.
The reaction was carried out under a nitrogen stream for a period of time. After completion of the reaction, the solid product was separated by filtration, washed with water and dried to produce Copolymer 1. Production Example 2 50 g of styrene, 30 g of isopropyl acrylate, 17 g of methyl methacrylate, and 3 g of monochlorovinyl acetate
Was used to produce Copolymer 2 in the same manner as in the synthesis of Copolymer 1. Example 1 70 parts of the resin of Production Example 1 30 parts of carbon black (Printex V manufactured by Degussa) were kneaded with a two-roll mill at 90 ° C. for 130 minutes and ground. 50 parts of the pulverized product lauryl methacrylate / methyl methacrylate / methacrylic acid / glycidyl methacrylate (80/10 /
5/5) 100 parts of Isopar H 20% solution of copolymer 100 parts of Isopar H (trade name of EXXSON) was put in a ball mill and dispersed for 24 hours. Then, 300 parts of Isopar H was further added and dispersed for 1 hour. This was a concentrated toner. Take 200 g of this, 50% Florinert FC-72 (Sumitomo 3M) and 50% KF96 (Shin-Etsu Silicone, viscosity 3cSt)
Was diluted in a mixed solvent 1 to obtain a developer. Example 2 57 parts of the resin of Production Example 2 250P (polyethylene manufactured by Sanyo Chemical Co., Ltd.) 8 parts 35 parts of MA60 (carbon black manufactured by Mitsubishi Kasei Co., Ltd.) were kneaded at 90 ° C. for 30 minutes by a flasher and then pulverized. 60 parts of the pulverized product stearyl methacrylate / methyl methacrylate /
Methacrylic acid / hydroxymethyl methacrylate (85/7
/ 4/4) 200 parts of Isopar H 10% solution of copolymer 100 parts of Isopar H was 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. 200 g of this was diluted in a mixed solvent 1 of 50% Florinert FC-72 (manufactured by Sumitomo 3M) and 50% Isopar H to prepare a developer. Example 3 60 parts of resin of Production Example 2 AC400A (manufactured by Allied Chemical) 10 parts Regal 400 (manufactured by Cabot) 30 parts were kneaded and pulverized with a flasher at 90 ° C. for 30 minutes. Thereafter, a developer was prepared in the same manner as in Example 1. An oil-less fixing test was performed using a testing machine in which the fixing unit of Ricoh CT5085 was modified to a hot roll fixing. The results are as shown in the following table. As is clear from the above results, the developer of the present invention provides a temperature range within a range in which the heat roller can be fixed without showing an offset phenomenon, and it can be seen that the heat roller can be fixed. In a closed room, continuous copying was performed using a test copying machine, and the solvent gas concentration was measured.The result was 300 to 360 ppm for the developer using only Isopar H as the carrier liquid, whereas the development according to the present invention Each of the preparations was halved to 80 to 150 ppm.

【effect】

By using the developer of the present invention, hot roll fixing can be performed without causing an offset phenomenon without applying oil to the fixing roll, and high-speed, low-energy fixing can be performed with a compact copying machine. . Also, the amount of hydrocarbon-based gas generated from the copying machine was reduced.

Continued on the front page (72) Inventor Hidemi Uematsu 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 9/13

Claims (1)

(57) [Claims] A toner particle comprising a colorant and a resin is dispersed in a carrier liquid having a high resistance and a low dielectric constant comprising a mixed liquid of a fluorine-based solvent, an aliphatic hydrocarbon solvent and / or a silicon-based solvent. A liquid developer for an electrostatic image, comprising, as at least a part of the resin, a copolymer consisting of a component composed of a monomer having an active halogen atom and a component composed of an acrylic monomer. Characteristic liquid developer for electrostatic images.