JP2000172021A - Production of liquid toner and liquid toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance productivity and quality by dry-comminuting specified colored chips and carrying out further wet comminution in a nonaqueous solvent. SOLUTION: A colorant, a resin and ionomer are heated and kneaded at a temperature above the softening point of the resin, the kneaded material is coarsely comminuted and the resulting colored chips are dry-comminuted and further wet-comminuted in a nonaqueous solvent. A pigment effective in prolonging the life of an interim transfer body as well as an ordinarily used pigment or dye may be used as the colorant. An acrylic resin such as a polyacrylic ester, a polyethylene type resin such as polyethylene or a mixture of such resins may be used as the resin. The ionomer is obtained, e.g. by neutralizing an ethylene-acrylic acid copolymer with a metal. A hummer mill, a jet mill or the like is used for the dry comminution. A media crusher such as an attriter, a sand mill or a mill can be used for the wet comminution without causing any trouble.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for producing a liquid toner applied to visualizing an electrostatic latent image, and to the liquid toner. For example, the present invention relates to a method for producing a liquid toner used as an image forming material of a color laser printer or a full-color digital on-demand printing machine, and a liquid toner thereof.

[0002]

2. Description of the Related Art In a system for realizing an electrostatic latent image, for example, in a full-color digital on-demand printer, a system using a powder toner and a system using a liquid toner have begun to appear on the market. Higher speed and higher image quality have been achieved compared to printers. Above all, liquid toner has a smaller particle size than powder,
This is advantageous for achieving high image quality. In addition, the point that the full-color digital on-demand printing machine is differentiating from the conventional printing machine is that the "on-demand"
Although it is a function such as "page variable", it is also important that it can be applied to various types of base materials required for conventional printing presses, and "intermediate transfer method" is adopted as a solution Some systems do.

[0003] As a method of producing a liquid toner, when roughly classified, there are a method emphasizing the treatment of a colorant and a method focusing on a method of producing toner particles. The former is for the purpose of maintaining image density and other image quality by dispersing pigments and the like as colorants without agglomeration, and the latter is a resin polymerization method, a kneading method with a colorant, a resin pulverizing method, There are various methods such as a dissolution precipitation method, and most of them are aimed at improving image quality. Among them, there are the following regarding the freeze grinding method. JP-A-7-234551 discloses that a thermoplastic resin as a binder component is freeze-pulverized and classified, and then wet-pulverized together with a colorant. This invention is intended to replace the process of heating and solvating a resin raw material with a solvent to solvate and then cooling and precipitating it to dry freezing and pulverization, and to achieve storage stability of the obtained intermediate composition and reduction of production cost. Although possible, it is disadvantageous to disperse the colorant in relatively hardened and ground resin powder, which may result in insufficient image density.

[0004] Japanese Patent Application Laid-Open No. 10-10796 discloses that toner particles are produced based on a pigment composition produced by kneading a pigment and a resin, followed by freeze-pulverization, and then dissolving and dispersing in a non-aqueous solvent. Has been described. JP-A-10-10797 describes that a pigment and a resin are kneaded, then frozen and pulverized, and then dissolved and dispersed in a non-aqueous solvent to prepare a pigment composition for a liquid toner. Further, there are the following using ionomer as a material of a liquid toner.

Japanese Patent Publication No. 9-500976 discloses that the chargeability is improved by coating liquid toner particles having poor chargeability with an ionomer.

[0006]

The liquid toner used as an image forming material for a color laser printer or a full-color digital on-demand printing machine is required to have a higher speed, a higher image quality and an improved liquid toner productivity. Higher speed and higher image quality are almost always achieved by improving the constituent materials of the particles. However, this alone is insufficient, and a new manufacturing method is required to improve the productivity of liquid toner, and the dispersing step of the colorant, the dissolving step of the resin, and the pulverizing step of the colored resin can be performed in a short time. There is a need for a method of producing high quality images with high speed and a liquid toner produced by the method.

[0007]

Means for Solving the Problems The present inventors added a colorant, a resin, and an ionomer, kneaded by heating, coarsely pulverized the resulting mixture, and dry-pulverized a colored chip, and further added a non-aqueous solvent. By performing wet pulverization with, a liquid toner having improved productivity and quality can be manufactured. The first invention is a method for producing a liquid toner, comprising adding a colorant, a resin and an ionomer, kneading under heating, dry-grinding the obtained colored chips, and further wet-grinding in a non-aqueous solvent. is there.

The second invention provides an ionomer obtained by neutralizing an olefin resin containing a carboxyl group with a metal by an acid value of 10%.
2. The method for producing a liquid toner according to claim 1, wherein the amount is 0 mgKOH / g or less. According to a third aspect, the weight average molecular weight of the ionomer is from 500 to 100.
00. The method for producing a liquid toner according to the first or second invention, wherein The fourth invention is the method for producing a liquid toner according to any one of the first to third inventions, wherein the dry pulverization is freeze pulverization. A fifth invention is the method for producing a liquid toner according to any one of the first to fourth inventions, wherein a charging aid is added during wet pulverization.

A sixth aspect of the present invention is applied to an image forming system in which an image formed by toner particles revealed on an electrostatic latent image carrier is transferred to an intermediate transfer member and finally transferred to a substrate. 5. A method for producing a liquid toner according to any one of claims 4 to 4.
A seventh invention is a liquid toner obtained by the method according to any one of the first to sixth inventions.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. The coloring chip heats and kneads the coloring agent, the resin, and the ionomer at a temperature equal to or higher than the softening point of the resin, and coarsely pulverizes the mixture. Next, the obtained colored chips are dry-pulverized and further wet-pulverized in a non-aqueous solvent to obtain a liquid toner. As the coloring agent used in the present invention, not only pigments and dyes which are usually used, but also pigments effective for extending the life of the intermediate transfer member may be used. To illustrate them,
Hansa Yellow, Disazo Yellow, Quinoline Yellow, Permanent Yellow, Isoindolinone, Benzidine Orange, Vengara, Fast Red, Lisole Red, Permanent Red, Watchyan Red Calcium Salt, Watchyan Red Manganese Salt, Quinacridone, Pyrazolone Red, Lake Red C , Lake Red D, Brilliant Carmine 3B or 6B, Navy Blue, Phthalocyanine Blue, Victoria Blue, Nigrosine, Carbon Black and the like. These colorants can be used alone or as a mixture. The content ratio of the pigment to the resin is preferably in the range of 0.1 to 50% by weight.

The resins used in the present invention include acrylic resins such as polyacrylates and polymethacrylates, polystyrenes, polyethylene-acrylic acid copolymers, polyethylene-methacrylic acid copolymers, and polyethylene-vinyl acetate copolymers. Polymer, Na salt, Zn salt, Ca salt of ethylene methacrylic acid copolymer, Na salt, Zn salt, Ca salt, Mg salt of ethylene acrylic acid copolymer, ethylene ethyl acrylate copolymer, ethylene maleate Use of polyethylene resin such as acid copolymer, other polyvinyl chloride resin, nitrocellulose, alkyd resin, phenol resin, polyester resin, polyvinyl butyral resin, polyisocyanate resin, polyurethane resin, polyamide resin, epoxy resin alone or in combination I do.

The ionomer is, for example, a product obtained by neutralizing an ethylene-acrylic acid copolymer with a metal, and is commercially available from Allied Signal under the trade name AClyn. There are Ca salt, Mg salt, Na salt, and Zn salt types, all of which have the effect of pigment dispersion. As the amount of addition, 0.01 to 10 parts can be added to 1 part of the pigment. The acid value is 100 m in consideration of the affinity with the resin.
gKOH / g or less, more preferably 6 gKOH / g or less.
It is 0 mgKOH / g or less, and may not have an acid value. Further, the weight average molecular weight is preferably in the range of 500 to 10,000. For the heating and kneading of the colorant, the resin, and the ionomer, a two-roll, twin-screw extruder, a Banbury mixer, or the like is used.

For the dry pulverization, a hammer mill, a jet mill, a pin mill, a turbo mill, a cutter mill, a ball mill, a vibration mill, a planetary mill and the like are used. In this case, the composition to be pulverized with liquid nitrogen or solid carbon dioxide is cooled, embrittled, and pulverized by a similar pulverizer. After the pulverization, coarse particles are removed using a classification device as necessary. By making the openings of the classifier finer in this classifying step, the time required for the next wet pulverizing step can be reduced. For wet milling, there are no problems with medial mills such as attritor, sand mill, dyno mill, ball mill, apex mill, spike mill, coball mill, diamond fine mill, pearl mill, DCP mill, aquamizer, micros, pure mill, NP mill, etc. It can be used, and in a medial crusher, a homogenizer, a trigonal, a slasher, a colloidal mill, a cavitron, a gatorol, a desper mill, an ebaramilder, a nanomizer, an aquatech, a myloider, etc. can be used if the amount of the ionomer of the present invention is slightly increased. .

In the present invention, the charging aid added during wet grinding is preferably a metal salt of a saturated fatty acid or a metal salt of an unsaturated fatty acid. For example, calcium stearate,
Aluminum stearate, aluminum laurate,
Barium laurate and sodium oleate are particularly preferred for charging toner particles and thus for electrophoresis. In addition, the timing of addition of the charging aid during wet pulverization may be any time from the start of pulverization to immediately before the end of pulverization. It is apparent that the latter has a higher electrophoretic property than the one in which the charging aid is added during the heat kneading and the one in which the charging aid is added during the wet pulverization. Therefore, it is preferable to add the charging aid during the wet pulverization.

The liquid toner according to the production method of the present invention is
A good reason for image formation in the copying method is that heating with a solvent
Liquid toner is eliminated because the step of solvation and precipitation is omitted.
Due to the small amount of solvent in the particles, the solvent
The heat that evaporates can be used to dissolve the toner particles.
The fixing property to the material is improved. Used for the liquid toner of the present invention
As the solvent, the dielectric constant is 3.5 or less, and the volume resistance is 10 or less. ⁷Oh
It is a hydrocarbon-based solvent with a centimeter or more. These preferred
As an example, it has a boiling point in the range of 150 to 220 ° C.
Aliphatic hydrocarbons and aromatic hydrocarbons
G, H, L (Exxon Chemical), Shersol A,
AB (manufactured by Shell), Naphthesol L, M, H (Nippon Oil
Manufactured).

The liquid toner of the present invention exhibits higher electrophoretic properties by adding a charge control agent. Not only surfactants which are usually used as charge adjusting agents for liquid toners, but also charge adjusting agents for high-speed printing can be used without any problem. For example, cobalt naphthenate, zinc naphthenate, copper naphthenate, manganese naphthenate, lecithin, cobalt octylate, zirconium octylate, alkyl allyl sulfonates, petroleum metal sulfonate,
Polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, phosphoric acid ester and the like can be used alone or in combination of two or more. Japanese Patent Application Laid-Open No. Hei 6-208255-7 and Japanese Patent Laid-Open Publication No. Hei 7-509
No. 074 can also be used.

The amount of addition is 0.1 to 5.5 in terms of solid content of toner particles.
It is appropriately added in the range of 0.01 to 50 parts to 1000 parts by weight of the developer.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. (Examples 1 to 5) Tables 1 to 5 corresponding to the symbols in Table 6 respectively.
A prototype was produced under the conditions shown in Table 5, and the results shown in Table 7 were obtained. Example 1 will be described below as a specific example. The carbon black pigment corresponding to the symbol A in Table 1, the resin ethylene-methacrylic acid copolymer corresponding to the symbol B in Table 1, and the symbol D in Table 2
The ionomer having an acid value of 42 mgKOH / g neutralized with Ca corresponding to the above is kneaded at 100 ° C. exceeding the softening point of the resin with two rolls corresponding to the symbol H in Table 4 in a mixing ratio according to Table 3, and It was coarsely pulverized into 10 mm square to obtain a colored chip.
Then, pulverize with a pin mill while cooling with liquid nitrogen,
When the particles were classified using a mesh having a mesh size of 150 microns, a pulverized product having an average particle size of 42 microns (SA-CP3L, a centrifugal sedimentation type particle size distribution measuring device manufactured by Shimadzu Corporation) and having a sharp particle size distribution was obtained.

The pulverized material was mixed according to the following formulation and wet pulverized by an attritor (Union Process). 25 parts of the above pulverized product 74 parts Isopa H (manufactured by Exxon Chemical Co.) 74 parts Aluminum stearate corresponding to symbol K in Table 5 1 part
3 L, liquid toner particles of a centrifugal sedimentation type particle size distribution analyzer manufactured by Shimadzu) were obtained. Further, since the liquid toner particles are not spherical but have a plurality of fibers, they correspond to “particle diameter” in Table 7 when measured with a light scattering diffraction type particle size distribution analyzer (SALD-2000A, manufactured by Shimadzu Corporation). The average particle size was 1 micron. The liquid toner particles are adjusted to a non-volatile content of 2.0% with Isopar H,
The liquid toner was obtained by adding 1.0 part of lecithin as a charge control agent to the parts.

The electrophoretic property is an evaluation of what is called particle conductivity, which is the difference between high electric field conductivity and low electric field conductivity. The conductivity of the particles alone means that the higher the particle, the more suitable it is for high-speed printing. The high electric field conductivity is:
Measured at 5 V / micrometer (DC), low field conductivity is measured at 5 V / mm (AC: 5 Hz). The measurement result was 150 pS as shown in “Electrophoresis” in Table 7.
/ Cm (pico siemens / cm). This liquid toner is used as a full-color digital on-demand printer E
-Print 1000 (manufactured by Indigo Corporation) was placed in a liquid toner tank, and the output voltage was fixed at 400 V, and the output image was evaluated.

The "image density" is defined as X-Rite 408 (X
-Rite) to obtain 1.78 in Table 7.
"Adhesiveness" is (tape peeling resistance) (rubber resistance to eraser)
The evaluation results of (claw scratch resistance) were totaled and evaluated on a 7-point scale to obtain 7 in Table 7 (the higher the value, the better). (Comparative Example 1) A prototype was produced and evaluated under the same conditions as in Example 1 except that no ionomer was added during kneading with two rolls. (Comparative Example 2) A trial production and evaluation were performed under the same conditions as in Example 1 except that the charging aid was added at the time of kneading with two rolls. (Comparative Example 3) Instead of freezing and pulverizing the colored chips, 60 parts of Isopa H (manufactured by Exxon Chemical Co., Ltd.) was stirred and heated and dissolved in 40 parts of the colored chips.
Attritor mixed with the following formula (Union Process)
A trial production and evaluation were performed under the same conditions as in Example 1 except that wet grinding was performed.

62.5 parts of the above precipitate 36.5 parts of Isopa H (manufactured by Exxon Chemical Co.) 1 part of aluminum stearate corresponding to the symbol K in Table 5 (Comparative Example 4) The carbon black pigment corresponding to the symbol A and the resin ethylene-methacrylic acid copolymer corresponding to the symbol B in Table 1 were dissolved by stirring and heating according to the following formulation, and then cooled and precipitated. Carbon black pigment 6 parts Ethylene-methacrylic acid copolymer 32 parts Isopa H (manufactured by Exxon Chemical Co.) 62 parts Then, the mixture was mixed according to the following formulation and wet-pulverized with an attritor (Union Process). A prototype was produced and evaluated under the same conditions as in Example 1.

62.5 parts of the above precipitates 36.5 parts of Isopa H (manufactured by Exxon Chemical Co.) 1 part of aluminum stearate corresponding to the symbol K in Table 5

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

[Table 7]

[0031]

By using the liquid toner produced by the production method of the present invention, an electrophoretic image having a high image density and a high fixing strength can be obtained in an electrophotographic printing system. , Increased productivity. Improvement in productivity is achieved by replacing the method of wet grinding with a colorant etc. after heating and dissolving / cooling and precipitating in a resin solvent, by replacing the method of heating and kneading the colorant etc. in advance,
Furthermore, a higher effect was obtained by performing dry pulverization without heating dissolution / cooling precipitation in a solvent thereafter.

To improve the electrophoretic property and the image density, the charge aid should be added during wet grinding, the ionomer of the present invention should be added, and the colored chips should be dry-ground without heating, dissolving and cooling in a solvent. The fixability was achieved by dry pulverization of a colored chip or resin in a solvent without heating, dissolving or cooling.

Claims (7)

[Claims] 1. A method for producing a liquid toner, comprising adding a colorant, a resin and an ionomer, kneading under heating, dry-grinding the obtained colored chips, and further wet-grinding in a non-aqueous solvent. 2. An acid value obtained by neutralizing an olefin resin containing a carboxyl group with a metal with a metal having an acid value of 100 mg KOH /
The method for producing a liquid toner according to claim 1, wherein the amount is not more than g. 3. The ionomer has a weight average molecular weight of 500.
3. The method according to claim 1, wherein the number is from 10,000 to 10,000.
A method for producing the liquid toner according to the above. 4. The method for producing a liquid toner according to claim 1, wherein the dry pulverization is freeze pulverization. 5. The method for producing a liquid toner according to claim 1, wherein a charging aid is added during wet pulverization. 6. The image forming system according to claim 1, wherein the image formed by the toner particles revealed on the electrostatic latent image carrier is transferred to an intermediate transfer member and finally transferred to a substrate. Or a method for producing a liquid toner according to the above. 7. A liquid toner obtained by the method according to claim 1.