JPH026962A - Metallic capsule toner and its production - Google Patents

Abstract

PURPOSE:To obtain metallic color tones by allowing a leaf-like material having metallic gloss near the surface of a core material. CONSTITUTION:The toner consists of core material particles contg. a coloring material and a core material covering said particles. The leaf-like material having the metallic gloss is made to exist as the 2nd coloring material near the surface of the core material particles. A flaky pigment (pearl pigment) formed by coating a leaf-like inorg. crystal with a thin layer consisting of titanium dioxide and metal aluminum pigment, etc., are usable as the leaf-like material having the metallic gloss. Since this pearl pigment has a laminar structure, the incident light on the inside of the fixed image is multiple-reflected regularly in the multilayered thin-layer films of the titanium dioxide formed on the leaf-like base body, by which the metallic gloss is obtd. The excellent metallic color tones are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a metallic capsule toner used in electrophotography, electrostatic printing, magnetic recording, and the like.

[Prior Art] As a toner used in the above-mentioned recording methods including electrophotography, pressurized toner is mainly used as an alternative to the conventional pulverization method toner, which is made by pulverizing a molten mixture of a binder resin and a colorant. Improvement of fixation [1]
As a target, various capsule-type toners have been proposed in which core particles are made of soft resin and a shell of hard resin is provided.

Various black and color capsule toners are known as such capsule toners, but no capsule toner having a metallic tone has yet been known.

- Regarding toners produced by force and pulverization methods, JP-A-62-10071 is known as a metallic toner.

[Problems to be Solved by the Invention] In the pulverization method, a substance that contributes to glossiness is added internally, so it is difficult to achieve its effect and a large amount must be added. Furthermore, since a large amount of such a substance is internally added, problems such as a decrease in fixing properties occur.

Furthermore, when attempting to produce sufficient metallic luster by using metal flakes as a substance imparting metallic luster, the electric resistance of the toner produced by the pulverization method decreases, making it difficult to obtain an insulating toner.

An object of the present invention is to provide a capsule toner having a metallic tone that can be applied to the recording methods mentioned above, including electrophotography, and a method for producing the same.

Another object of the present invention is to provide an electrophotographic toner that has good fixing properties on plain paper at a lower pressure or lower temperature than conventional ones, and has a glossy appearance with an excellent metallic tone decoration. It is in.

Another object of the present invention is to provide a capsule toner that maintains its initial characteristics even when used continuously over a long period of time, and does not cause toner aggregation or change in charging characteristics.

Another object of the present invention is to provide a capsule toner that provides images with vivid colors.

Still another object of the present invention is to provide an efficient method for manufacturing the capsule toner as described above.

Still another object is to provide a microcapsule toner that can impart metallic luster to the toner even when a small amount of a metallic luster imparting agent is used.

[Means and effects for solving the problems] The capsule toner of the present invention was developed to achieve the above-mentioned object, and comprises core particles containing a colorant and a shell covering the core particles. It is characterized by having a flaky substance with metallic luster present as a second coloring material near the surface of the siliceous core material particle.

Further, the capsule toner manufacturing method of the present invention includes externally adding and mixing resinous core material particles and a flaky material to adhere the flaky material to the surface of the core material particles, and forming core material particles to which the flaky material is attached. It is characterized by being covered with shell material resin.

When core material particles to which a flaky substance with metallic luster is attached by external addition and mixing are coated with shell material resin, the thickness required for the shell material of capsule toner is generally 0.05~
Since it is as thin as about 0.5p, its essential effects can be exerted in small amounts.

Further, it is known that the presence of inorganic fine particles near the core material is effective in providing a capsule toner without toner aggregation or change in charging characteristics, and stable images can be obtained.

The flaky substance with metallic luster that is externally added to the surface of the core particle of the present invention includes a flaky pigment (pearl pigment) made by coating IX1 flaky inorganic crystal-L with a thin layer of titanium dioxide, and metallic aluminum. Substances with metallic luster such as pigments can be used.

The action of this pearl pigment is that since this pigment has a layered structure, the light incident on the fixed image undergoes multiple regular reflections within the multiple thin layer film of titanium dioxide formed on the flaky substrate. It has a metallic luster (pearl luster).

When such a pearl pigment having metallic luster is present near the surface of the core material particle, it harmonizes with the color tone of the coloring material added inside the core material, and efficiently produces a fixed image with an extremely oil-like metallic tone. be able to.

As the material for the core particles used in the present invention, any soft solid substance that exhibits favorable fixing properties can be used. Such substances include waxes (beeswax, carnauba wax, microcrystalline wax, etc.), higher fatty acids (stearic acid, etc.).

palmitic acid, lauric acid, etc.), higher fatty acid metal salts (
aluminum stearate, lead stearate, barium stearate, magnesium stearate, zinc stearate, zinc palmitate, etc.), higher fatty acid derivatives (
methyl hydroxystearate, glycerol monohydroxystearate, etc.), polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polyisobutylene, polytetrafluoroethylene, etc.),
Olefin copolymer (ethylene-acrylic acid copolymer,
Ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-
(vinyl acetate copolymer, ionomer resin, etc.), styrene resin (low molecular weight polystyrene, styrene-butadiene copolymer, (monomer ratio 5-30:95-70)
styrene-acrylic compound combination, etc.), epoxy resin, polyester resin (acid value 1O or less).

Rubbers (inbutylene rubber, nitrile rubber, chlorinated rubber, etc.), polyvinylpyrrolidone, polyamide, coumaron
Indene resin, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.

There are silicone resins and the like, and these can be used alone or in combination.

The core particles of the capsule toner of the present invention generally contain various dyes and pigments as blue agents. Such dyes and pigments include, for example, carbon black, nigrosine dye, lamp black, Sudan Blank SM, Fast Yellow, Benzidine Niro, Pigment Yellow, Indofurth I...Orange, Irgadine Red, and Rose. Nitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Lysol Red 2G, Lake Red C, Rhodamine FB, Rhodamine B Lake.

Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Prilliant Green B, Phthalocyanine Green, Oil Yellow GG, 4f Hon.
First Niro 10GG, Kayase, l= Y2O2
, Kayaset YG, Sumiplast Yellow GG, Zapon First Orange RR, Oil Scarlet I, Sumiplast Orange G, Oran Ru Brown B, Pomegranate First Scarlent CG, Eisens Viron Red BED, Oil Pink OP, etc. are applicable. can.

In order to use the toner as a magnetic toner, magnetic powder may be contained in the five-core material particles. Such magnetic powder is a substance that is magnetized when placed in a magnetic field, and includes powders of ferromagnetic metals such as iron, conoheld, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of this magnetic powder is preferably 15 to 70% by weight based on the weight of the toner.

The core material particles of the capsule toner of the present invention include 1; the following components;
For example, melt kneading and granulating with a spray dryer etc.
Further, by classifying as necessary, fine particles having a volume average particle diameter of 5 to 20 μm are prepared.

A flaky substance is externally added and mixed to the core material particles obtained as described in I-, and is adhered to the surface of the core material particles.

Cloud n1. Crystals having a layered structure that can be opened at the arms, such as barium sulfate or layered silicates, can be used. By stacking such thin layers of crystals, a unique luster, i.e., pearlescent luster, is obtained by adding interference colors to the reflected light.

The formation of a titanium dioxide thin film to be coated on the above-mentioned inorganic flaky substrate-L is known.
It is obtained by hydrolyzing a titanium compound solution in which is dispersed.

The particle size of the flaky material used in the present invention is smaller than that of the core material particles, and has a =J' method.

In the present invention, these flaky substances include coffee grinders,
Using a powder mixer or a pulverizer such as a pulverizer or Henschel, the mixture is externally added to the core material particles, preferably under heating at about 40 to 50°C, and then encapsulated.
The amount added is from 08 to 60% by weight, preferably from 0.1 to 50% by weight, based on the core material particle weight i. 1-%, particularly preferably in the range 1-10% by weight. By such an external addition mixing operation, the flaky substance is attached in the form 79 embedded in the surface or surface layer of the core material particles.

Core material particles to which the flaky material obtained as described in L is attached, or an externally added mixture of core material particles and flaky material,
Cover with shell resin.

As the shell material resin, known resins can be used, such as resins made of the following monomers. Styrene and its substituted products such as styrene, P-chlorostyrene, and P-dimethylamino-styrene; methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, N, N methacrylate - Esters of acrylic or methacrylic acid such as dimethylaminoethyl ester; maleic anhydride or half esters, half amides or diesterimides of maleic anhydride, vinylpyridine, N
- Nitrogen-containing vinyls such as vinyl imidazole; vinyl acetals such as vinyl formal and vinyl butyral; vinyl monomers such as vinyl chloride, acrylonitrile, and vinyl acetate; vinylidene monomers such as vinylidene chloride and vinylidene fluoride; olefin monomers such as ethylene and fluoride; be. Also polyester, polycarbonate, polysulfonate, polyamide, polyurethane, polyurea, epoxy resin.

R1 of rosin, modified rosin, terpene resin, phenolic resin, saccharine or alicyclic hydrocarbon resin, aromatic petroleum resin, melamine resin, polyether resin or thioether resin such as polyphenylene oxide, etc.
i Monopolymers, copolymers, or mixtures can be used.

To obtain a capsule toner having an outer shell made of these polymers,
Various known encapsulation techniques can be utilized.
For example, spray drying method.

Coacervation method, phase separation method, etc. can be suitably used, as well as 1n-situ polymerization method, U.S. Patent No. 3.338.
．． 991 No.'511411 Fortune, +'in No. 3,32
No. 6,848 EJIMBm, No. 3,502,582
The method described in the specification can also be used.

Encapsulation by a phase separation method in 41t is preferred.

The capsule toner of the present invention thus obtained generally has the following characteristics:
It has an outer shell with a thickness of 0.05 to 0.5 tiles, and a volume average particle size of 6 to 22. become microcapsules.

In addition, a flaky substance is present near the surface of the core material grain -r. Here, the term "near the surface of the core particle" in which flaky substances exist refers to the surface of the core particle (interface with material a) and the surface layer at a depth within 115 mm of the diameter of the core particle. 90% or more of flaky material within, especially 8
A state in which 5% or more is present is preferable.

Furthermore, the capsule toner of the present invention has a volume resistivity of IQI.
The volume resistivity referred to here, which is preferably an OΩC layer or more, particularly a 1012ΩC layer or more, is a toner of 100k.
Molded at a pressure of g/ctm2, Koreni 100v/C11
It is defined as the value calculated from the current value one minute after applying an electric field.

As mentioned above, the capsule toner of the present invention is further added with carbon black, various dyes and pigments, hydrophobic colloidal silica, etc. for charge control, fluidity, coloring, etc. It is possible to stably exhibit the effects of their addition. The appropriate amount of these external additive components is about 0.1 to 5 parts per 100 parts of the capsule toner.

[Example] Hereinafter, the present invention will be explained by giving specific examples.

Example 1 Core material is Hiwax 200P (manufactured by Mitsui Petrochemical)
20 parts, paraffin wax 155 (made of 8-wood wax) 80
By melt-mixing 5 parts of phthalonanine blue at 150°C, granulating it with a spray dryer, and performing dry classification, a spherical core material with a particle size of 10.3p ± 5.0t was obtained. Particles were obtained.

−・Method, silica fine powder synthesized by dry method (specific surface area:
About 13.01 m1/g) 100 parts by weight of amine-modified silicone oil having an amine in the side chain (2
Viscosity at 5°C 70 cps, ifi per amine: 83
0) Spray 12 f, 113 parts and bring the temperature to approx.
The temperature was kept at 0°C and the treatment was carried out for 60 minutes.

7) Add 740g of pearl IyO to 1kg of core material particles described in 1j.
were externally added and mixed using a Henschel mixer model 10B (Mitsui Miike Seisakusho) at room temperature and 39 BO rpm for 3 minutes.

Next, the above externally added mixture of core material particles and pearl pigment was mixed with styrene-dimethylaminoethyl methacrylate (mole ratio 90/10) copolymer to a film thickness of 0.411 using a phase separation method from the organic phase. Coating was performed to obtain encapsulated particles. To 100 g of the obtained encapsulated particles F, - Fine silica powder 1 treated with the above amino-modified silicone oil
．． Further, 0 g was externally added and mixed in the same manner as above to obtain a capsule toner.

To 12 g of this capsule toner, 88 g of carrier (EFV250/400 manufactured by Nippon Steel Powder Co., Ltd.) was mixed as a developer to develop a latent image having a negative electrostatic charge, and then transferred onto high-quality paper. From both ends of the transfer paper with the toner image,
When the film was passed through a pressure fixing device consisting of two pressure rollers capable of applying pressure, it showed almost perfect fixing performance at a linear pressure of 10 kg/cmz.

The image obtained with this capsule toner was metallic blue with metallic luster and had good fixing properties.Example 2 The same operation as in Example 1 was carried out except that the internally added colorant was changed to pigment yellow. repeated.

As a result, as in Example 1, a metallic yellow image with metallic luster and good fixability at low or low temperatures was obtained.

Example 3 The same operation as in Example 2 was repeated except that the pearl pigment externally added to the core material particles was changed to a metal aluminum pigment (Alpaste 12130M + Toyo Aluminum) 2.0.

As a result, a golden capsule toner with metallic luster and good fixing properties was obtained.

Comparative Example 1 A pulverization method toner was prepared in which the main binder was a styrene-acrylic copolymer to which the same weight part of pearl pigment as in Example 1.2 was added.

This toner was used to develop a latent image in the same manner as in Example 1, and then transferred onto 1-quality paper. Next, a fixed image was obtained using a heat fixing machine.

The image thus obtained had poor metallic luster.

Comparative Example 2 The same procedure as Comparative Example 1 was carried out except that twice the weight of the added pearl pigment was used.

The resulting image had improved metallic luster compared to Comparative Example 1, but had poor fixability.

Comparative Example 3 Added pearl pigment to metallic aluminum pigment (Alpace) 1
Comparative Example 2 was carried out in the same manner as Comparative Example 2 except that the material was changed to 2EfOM+Toyo Aluminum).

The resulting toner had low electrical resistance and was unsuitable as a toner for electrophotography.

[Effects of the Invention] As described in 1- below, according to the present invention, a metallic capsule toner that has a more emphasized metallic tone and is used in electrophotography, static printing, magnetic recording, etc. is provided. .

Claims (1)

[Claims] 1) A capsule toner consisting of a core material particle and a shell material covering the core material, wherein a metallic capsule is characterized in that a flaky material having metallic luster is present near the surface of the core material. toner. 2) The metallic capsule toner according to claim 1, wherein the flaky material is a flaky inorganic crystal matrix coated with a thin layer of titanium dioxide. 3) Externally adding and mixing resinous core material particles and flaky material to adhere the flaky material to the surface of the core material particles, and covering the core material particles to which the flaky material is attached with shell material resin. A manufacturing method for a distinctive metallic capsule toner.