JPH0383080A - Electrostatic image transfer method, and liquid developer and electrostatic image recording body used therefor - Google Patents

Abstract

PURPOSE:To directly shift a pattern on an electrostatic recorder and to fix the pattern by forming an electrostatic latent image on the electrostatic recording body, developing the image with a liquid developer and transferring it to a material to be transferred. CONSTITUTION:An electric field is caused to act on an electrostatic recording body such as electrostatic recording paper, electrostatic recording synthetic paper and electrostatic recording film to directly form an electrostatically charged image. This image is developed with a liquid developer containing pigment and/or dye, and transferred onto the material to be transferred. Consequently, an electrostatic image obtained by developing an electrostatic latent image can be formed in a short time without requiring not only a plate making stage but also an original or film. Moreover, wide patterns can be consecutively obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an electrostatic recording method in which an electric field is applied to an electrostatic recording medium to directly form an electrostatic charge image, and this is developed to form an image. This invention relates to a novel electrostatic image transfer method that combines the advantages of liquid developer, such as high resolution, and to a liquid developer and electrostatic image recording medium used in the method.

[Conventional technology]

2. Description of the Related Art Conventionally, as a method of forming designs on metal plastics, glass, etc., a method is known in which a film is produced from an original document, a film is passed through a plate-making process, and a design is formed using a printing machine.

The above-mentioned pattern forming method involves many production processes such as complicated plate-making process depending on the number of colors, ink mixing, printing process, drying, etc., which results in large production losses and is not suitable for high-mix, low-volume production.
For example, due to the recent diversification of user needs, it has not been possible to adequately meet the industry's demands for quickly obtaining desired designs.

[Problem to be solved by the invention]

An object of the present invention is to provide an electrostatic image transfer method that can directly form an electrostatic image on an electrostatic recording medium, develop and fix it, and transfer a pattern to a transfer material such as metal, without providing a printing process. It is.

Another object of the present invention is to provide an electrostatic image transfer method that does not require a plate-making process and can form patterns not only when using a manuscript but also by computer operation.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention includes a first step of directly forming an electrostatic charge image by applying an electric field to an electrostatic recording medium, and a step of directly forming an electrostatic charge image by applying an electric field to an electrostatic recording medium. Alternatively, there is provided an electrostatic image transfer method characterized by comprising a second step of developing with a liquid developer containing a dye, and a third step of transferring the developed image to a transfer material.

The present invention also provides a liquid developer used therein and an electrostatic recording medium having a pattern obtained by developing and fixing an electrostatic latent image.

Next, the present invention will be explained in detail.

In the present invention, wet electrostatic recording type monochrome and color electrostatic plotters, facsimiles, and the like are preferably used to directly form an electrostatic image by applying an electric field to the electrostatic recording medium. In particular, when an electrostatic plotter is used, an electrostatic latent image corresponding to a pattern stored as data in a computer can be directly imprinted onto an electrostatic recording medium, and an image can be output. This not only eliminates the need for a plate-making process, but also eliminates the need for manuscripts and film as in conventional printing methods, making it possible to obtain electrostatic images with developed electrostatic latent images in a short period of time. You can also get it, and you can get it continuously. Of course, a manuscript can also be used.

Examples of the electrostatic recording medium used in the present invention include commercially available electrostatic recording paper, electrostatic recording medium, electrostatic recording film, and the like.

The electrostatic latent image formed on the electrostatic recording medium is developed, and a developing method includes a method in which the surface of the electrostatic recording medium on which the electrostatic latent image is formed is brought into contact with a liquid developer. This liquid developer can be obtained by using pigments and/or dyes conventionally used as components of liquid developers for electrostatic latent images. Furthermore, if necessary, it is composed of a mixture with auxiliary agents such as a charge control agent and a dispersion stabilizer.

Conventionally known dyes and/or pigments can be used, such as carbon blank, spirit black, aniline black, oil blank, nigrosine, wool blank, blue black E1 alkali blue, phthalocyanine blue oil blue, acid blue. , cyanidin blue Victoria blue, methylene blue, chrysoidine, soutane high olent, crystal violet, oil violet, methyl violet, phthalocyanine green, acid black green, malachite green, safranin, brilliant carmine 6
B, Rhodamine 6G, Fast Red, Oil Red, Congo Red, Auragon, Rhodamine B1 Barium Red 2B, Calcium Red 2B, Strontium Red, Manganese Red 2B, Barium Solelet, Calcium Red 52, Lake Red C1 Formaloon L-58, Brilliant Car ξn 3B, Brilliant Scarlet G, Quinacridone Magenta, Bismalek Brown, Benzidine Yellow, Hansa Yellow, Fast Yellow G1 Fast Yellow 10G, Disazo Yellow AAA, Disazo Yellow AAMX, Disazo Yellow AAOT, Disazo Yellow AADA, Isoindolinone Yellow 2GLT, Isoindolinone Yellow 3RLTN, Benzimidacilone Yellow 83G
, Benzimidacilone Yellow 1 (4G, etc.). Commercially available products include, for example, Kayaset Yellow ^-G, Kayase Ntore Ndo B, manufactured by Nippon Kayaku Co., Ltd.
Kayase Netfil-FB, Kayaseron Yellow E-5
GSE-3GL, E-HGL, Kayaron Red E-GL E-BP, E-2BL, Kayaron Blues Blue E-GL, Kayaron Navy Blue E-EX
.

Kayalon Black E-EX, Kayalon Brilliant Flavin GL-3F, FG-S, Kayalon Light Yellow 5GS, Kayalon Yellow HGL-3FSYL-
5R, 4R-E.

PAL-E, Kayalon Red 0R-3SAD-3,,
TL-SP.

BL-E, 4L-SF, PAL-E, Kayalon Blue 3R-5F.

CR-E200.2R-SF,,GR-E,,EBL
-E, PAL-E, Kayalon Brilliant Blue F
R-S, F2B-3, Kayalon Torquees Blue GL
-S200, Kayalon Navy Blue GX-5F20
0. Kayalon Black 5200, BR-3F, EX-5
F200; Sumikalon Brilliant Flavin S-10G manufactured by Sumitomo Chemical Co., Ltd., Sumikalon Yellow 5E-5G
.

5R-3GLconc, , 5E-RPD, E-RP
O, S-R, 5-RPD.

Sumikaron Orange 5R-RPD, S-R, Sumikalon Red E-3BR, 5-BDF, E-RPD
,,E-FBL, 5-BLP.

5-RPD, 5-BP, Sumikalon Blue S-3R
F, E-GRL.

5R-RF, E-R, E-BL, E-FBL,
, E-RPD 5S-BG.

5E-RPD, Sumikalon Blank 5-BL, E-B
(N) etc.

As the fixing agent for the liquid developer used in the present invention, any known fixing agent can be used without particular limitation. Particularly suitable fixing agents include the following.

(1) An acrylic copolymer soluble in an electrically insulating carrier liquid, comprising methyl methacrylate and an acrylic acid ester or a long-chain alkyl ester of methacrylic acid, as described in Japanese Patent Publication No. 49-20996.

(2) A first polymer chain made of a vinyl polymer soluble in an electrically insulating carrier liquid and a second polymer chain made of a vinyl polymer insoluble in the carrier liquid described in JP-A-58-122557. A non-gel-like graft polymer having a molecular structure in which molecular chains are mutually bonded through urethane bonds, and the entire molecule is insoluble in the carrier liquid.

(3) a crosslinked polymer soluble in an electrically insulating carrier, which is prepared by crosslinking a vinyl polymer having an active hydrogen atom capable of reacting with an isocyanate group with a polyisocyanate compound, as described in JP-A-59-34540; A w1 chain polymer comprising a vinyl polymer insoluble in the carrier liquid, which is captured by the crosslinked polymer due to mutual entanglement of molecular chains.

(4) A crosslinked polymer (hereinafter referred to as a crosslinked polymer) soluble in an electrically insulating carrier liquid, which is obtained by crosslinking a vinyl polymer having a crosslinking-reactive functional group in its molecular side chain, as described in JP-A No. 63-208866. A vinyl copolymer insoluble in the carrier liquid is formed by copolymerizing a vinyl monomer having a basic nitrogen atom or an amide group in the molecule with a vinyl acetate monomer. Examples of the polymer include a threaded chain polymer that is captured by the crosslinked polymer due to mutual entanglement of molecular chains.

Examples of the electrically insulating carrier liquid include hexane, pentane, octane, nonane, decane, undecane, and dodecane, as well as Isopar manufactured by Esso Standard Oil Co., Ltd.
having a boiling point in the temperature range of 100 to 250°C, such as organic solvents sold under trade names such as H, L, M, etc.
Various aliphatic hydrocarbon solvents having a volume resistivity of 10'' Ω·cm or more and a dielectric constant of less than 3 can be used.

In the present invention, the mixing ratio of the pigment and/or dye and the fixing agent is preferably in the range of 5 to 500 parts by weight per 100 parts by weight of the fixing agent. If the amount of pigments and dyes exceeds 500 parts by weight per 100 parts by weight of the fixing agent, toner particles tend to aggregate when uniformly dispersed to prepare a liquid developer, and the dispersion stability of the resulting image forming agent deteriorates. There is a tendency to deteriorate, and the fixing agent 100
If the amount of pigments and dyes is less than 5 parts by weight, it is not preferable because sufficient image density tends not to be obtained.

The liquid developer according to the present invention is prepared by adding a mixture of a pigment and/or dye, a fixing agent, an electrically insulating carrier liquid, and further auxiliary agents such as a charge control agent and a dispersion stabilizer as necessary to a ball mill, a sand mill, an attritor, etc. Prepare a concentrated toner having a non-volatile content of about 10% by uniformly dispersing it with the carrier liquid, and then diluting this condensed toner with the carrier liquid so that the non-volatile content is about 0.1 to 2%. I can do it.

As auxiliary agents such as charge control agents and dispersion stabilizers, any of those commonly used in liquid developers for developing electrostatic latent images can be used, such as cobalt naphthenate, copper naphthenate, copper oleate, Examples include cobalt oleate, zirconium octylate, cobalt octylate, and aluminum stearate. Further, waxes such as paraffin wax, polyethylene wax, polypropylene wax, ethylene copolymer, and propylene copolymer, nonionic surfactants, anionic surfactants, and cationic surfactants can also be used.

In the present invention, in order to transfer the developed image obtained on the electrostatic recording medium using the liquid developer to the transfer material such as metal, the developed image is transferred to an aluminum plate at a temperature of 160° C. ~220°C for a short time, e.g. 10-60
Just hold the contact for a second.

In order to perform the transfer efficiently, it can also be carried out continuously under pressure or reduced pressure. Also, the transferred image may be coated with resin or 5. The design may be protected by laminating the film. When transferred in this way, the colorant in the liquid developer and the resin used in the fixing agent are transferred to Aluminum
Since it is transferred to the board and fixed, there is no need for a plate-making process or a printing process.

There is no limit to the transfer material used in the present invention;
Examples include metal foils of aluminum, iron, copper, etc., metal plates and metal cans, plastics such as polypropylene, polyethylene, and glass.

[Examples] Hereinafter, the present invention will be explained in more detail according to Examples.
Tokimei is not determined by these things.

(Production of fixing agent) (1) Fixing agent A: 150 parts by weight of kerosene was charged into a glass container equipped with a reflux condenser, heated to 90'C while stirring, and mixed with 15 parts by weight of methyl methacrylate and methacrylic acid-2. Chilhexyl 8
A monomer solution prepared by dissolving 0.5 parts by weight of benzober peroxide in a mixture with 5 parts by weight was added dropwise over a period of 4 hours. Thereafter, it was heated to 100°C at a temperature increase rate of 1°C/3 minutes and maintained at this temperature for an additional 4 hours. After cooling, the contents were taken out to obtain a viscous resin solution with a viscosity of 20 to 100 Stokes. The resin solution thus obtained is referred to as "fixer A".

(2) Fixing agent B 30.0 parts by weight of lauryl methacrylate, 22.0 parts by weight of butyl methacrylate, 46.6 parts by weight of butyl acrylate, 0.4 parts by weight of hydroxypropyl methacrylate, 1.0 parts by weight of methacrylic acid. , "Barbutyl DJ (polymerization catalyst manufactured by NOF Corporation) 1.0 parts by weight and "ISOPAR GJ100
Part by weight was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, and a cooling tube, heated to 120°C, and reacted at 120°C for 8 hours to obtain a non-volatile content of 48.8% and an average molecular weight of 2.
A heavy content of 20,000 was obtained.

Next, the temperature was lowered to 70°C, 0.62 parts by weight of isophorone diisocyanate, 0.05 parts by weight of tin-octylate, and 0.61 it part of "Isopa G" were added, and the mixture was heated to 70°C.
The urethane reaction was carried out for 4 hours and then cooled to obtain a solution of an intermediate containing isocyanate groups with a non-volatile content of 48.6% and an NC content of 0.6%.

106 parts by weight of the solution of the intermediate was charged into the same reaction vessel as above, and 180 parts by weight of Isopar GJ, 0.4 parts by weight of hydroxypropyl methacrylate, 46.1 parts by weight of methyl methacrylate, and abbisisobutyronitrile were added. 0.251 i part was added, the temperature was raised to 80°C, and the mixture was reacted at 80"C for 5 hours to obtain a graft polymer solution having a non-volatile content of 29.2% and an NCO content of 0%. This graft polymer is a white latex in which a first polymer chain and a second polymer chain are bonded by about 6 urethane bonds per molecule. The polymer solution obtained in this way is called "Fixer B".
shall be.

(3) Fixing agent C 80 parts by weight of lauryl methacrylate, 2-methacrylic acid
10 parts by weight of hydroxyethyl, 1 part by weight of N-vinylpyrrolidone
0fiit part, 1 part by weight of G-ter t-butyl peroxide, and 48 coulometric parts of Isopar G jl were charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, and a cooling tube, and the temperature was raised to 130 ''C. Raise the temperature to 1.
The reaction was carried out at 130'C for 6 hours to obtain a solution of the first polymer. The temperature was then lowered to 80°C, and 1.5 parts by weight of isophorone diisocyanate and 0 parts of di-n-butyltin dilaurate were added.
．． Add 03 parts by weight and 32 parts by weight of Isopar s
The urethane reaction was carried out at o'c for 2 hours and cooled to obtain a crosslinked polymer solution with a non-volatile content of 38.2%.

131 parts by weight of the crosslinked polymer was charged into a reaction vessel similar to the above, and further added with 152 parts by weight of Isopar GJ, 5 parts by weight of 2-hydroxypropyl methacrylate, 40 parts by weight of methyl methacrylate, and 5 parts by weight of β-methacryloxyethyl phthalate.
parts by weight and 0.25 parts by weight of abbisisobutyronitrile were added, the temperature was raised to 80'C, and the reaction was carried out at 80°C for 6 hours to obtain a solution of a stranded polymer with a non-volatile content of 30%. The solution of the chain polymer obtained in this way is called "Fixer C".
shall be.

Example 1 “Kayaset Red B J 100 parts by weight (
Disperse dye manufactured by Nippon Kayaku Co., Ltd.) 300 parts by weight of the fixing agent A Cobalt naphthenate 16 weight 11B (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: Cobalt naphthinate 6%) Isoparaffinic hydrocarbon 900 parts by weight (manufactured by Exxon Chemical Co., Ltd., (Product name: Isopar G) A concentrated toner was prepared by uniformly mixing and kneading the above dye, fixing agent, charge control agent, and carrier liquid in a ball bowl.

This concentrated toner was diluted with the above-mentioned isoparaffinic hydrocarbon (trade name: Isopar G, manufactured by Exxon Chemical Co., Ltd.) to a non-volatile content of 12% by weight, and 80 parts by weight of the paste donor was further diluted with 2000 parts by weight of the above-mentioned isoparaffinic hydrocarbon, and liquid development was performed. The drug was manufactured.

Next, an electrostatic latent image was formed on an electrostatic recording film (trade name: Kymograph EPF, manufactured by Kimoto Co., Ltd.) using an electrostatic block-rEP-101, 4 manufactured by Matsushita Densen Co., Ltd., and developed with the liquid developer described above. The obtained image was adhered to an aluminum plate (aluminum alloy JIS3004 manufactured by Kobe Steel) and
After heating at 'C for 30 seconds, the electrostatic recording film was peeled off. A clear red pattern was obtained on the aluminum plate.

Example 2 “Mogul L J 100 parts by weight (
8,400 parts by weight of the above-mentioned fixing agent (pigment manufactured by Cabot, USA) 16 parts by weight of zirconium naphthenate (manufactured by Nihon Kagaku Sangyo Co., Ltd., trade name Nikka Octix Zirconium) 600 parts by weight of isoparaffinic hydrocarbon (manufactured by Exxon Chemical Co., Ltd., trade name Isopar G) A liquid developer was prepared in exactly the same manner as in Example 1 using the above pigment, fixing agent, charge control agent, and carrier liquid, and development was performed.

By processing the obtained image in exactly the same manner as in Example 1, a black pattern was obtained on the aluminum plate.

Example 3 In Example 2, except that phthalocyanine blue (manufactured by Dainippon Ink & Chemicals, trade name: First Gen Blue TGR) was used instead of "Mogul L" and the fixer C was used instead of fixer B. A liquid developer was produced in the same manner as in Example 2, and development was performed.

By processing the obtained image in exactly the same manner as in Example 1, a blue pattern was obtained on the aluminum plate.

Example 4 Example 3 except that ``Shimura First Yellow 4193G J (yellow pigment manufactured by Dainippon Ink & Chemicals ■) was used instead of phthalocyanine blue.
A liquid developer was prepared in the same manner as above, and development was performed.

By processing the obtained image in exactly the same manner as in Example 1, a yellow pattern was obtained on the aluminum plate.

〔Effect of the invention〕

According to the present invention, an electrostatic latent image is formed on an electrostatic recording medium, developed with a liquid developer, and further transferred to a transfer material such as a metal material, so that the pattern on the electrostatic recording medium is transferred. It can be fixed by using the same method, and there is no need for a plate-making process or a printing process as in the past. Moreover, since designs can be drawn by computer operation, it is suitable for high-mix, low-volume production, and wide designs can be produced continuously, making it possible to create unique designs, such as the exterior designs of recent aluminum cans. It is possible to respond flexibly and quickly to various demands for differentiation, and to supply these at low cost.

Claims (1)

[Claims] 1. (1) A first step of directly forming an electrostatic charge image by applying an electric field to an electrostatic recording medium, and (2) forming the electrostatic charge image containing a pigment and/or a dye. An electrostatic image transfer method comprising: a second step of developing with a liquid developer; and (3) a third step of transferring the developed image to a transfer material. 2. A liquid developer used in the electrostatic image transfer method according to claim 1. 3. An electrostatic image recording material having a pattern obtained by developing and transferring the electrostatic image according to claim 1.