JPH06110255A - Dry two-component developer - Google Patents

Abstract

(57) [Summary] [Object] The present invention relates to a dry two-component developer of a toner containing a carrier coated with a silicone resin and a metal complex used in electrophotography, electrostatic printing, etc. Adhesion to the coating layer is good, there is no film abrasion, and toner
The present invention provides a dry type two-component developer which can freely control the charge amount of N. In a two-component developer comprising a carrier and a toner, carrier particles having a coating layer containing a silicone resin and an aminosilane coupling agent as a main component on the surface, and a salicylic acid metal salt and / or salicylic acid as a charge control agent Toner particles containing a metal salt of a derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic developer used in electrophotography, electrostatic printing and the like.

[0002]

2. Description of the Related Art Two-component dry developers using carrier particles coated with silicone resin are well known. However, since the coating layer was thin, the film was scraped off and the life was not long. When the carrier particles are combined with a toner containing a metal salt of salicylic acid metal and / or a salicylic acid derivative, the toner is negatively charged, or the silicone resin itself is negatively charged due to the triboelectric charging series. In addition, it was difficult to control the charge controllability of the toner.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dry two-component developer using carrier particles provided with a silicone resin as a coating layer, which has good adhesion between the core material and the resin and prevents film abrasion. -To provide a two-component developer capable of freely controlling the negative charge amount.

[0004]

In order to achieve the above object, the present invention provides carrier particles having a coating layer containing a silicone resin and an aminosilane coupling agent as main components, and a salicylic acid metal salt as a charge control agent. And / or toner particles containing a metal salt of a salicylic acid derivative, and a dry two-component developer.

The present invention will be described in more detail below. The silicone resin that can be used for the carrier coating layer in the present invention is a silicone resin generally known in this field or a modified product thereof. As commercial products, there are KR271, KR255, KR251 manufactured by Shin-Etsu Chemical Co., Ltd., SR2400, SR2406 manufactured by Torre Silicone Co., Ltd., and as the modified silicone resin, KR206 manufactured by Shin-Etsu Chemical Co., Ltd.
(Alkyd resin modified product), KR3093 (acrylic resin modified product), ES1001N (epoxy resin modified product),
There are SR2115 (epoxy resin modified product) and SR2110 (alkyd resin modified product) manufactured by Torre Silicone. It is appropriate that the coating amount of the silicone resin is about 0.5 to 50 parts by weight per 100 parts by weight of the carrier core material.

The aminosilane coupling agent added to the silicone resin coating layer is typically represented by the following general formula (1)
X-Si (OR) ₃ (1) X is a functional group having an amino group, and R is a hydrolyzable group. Examples of aminosilane coupling agents include γ
-(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aninopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, etc. Is mentioned. The presence of the aminosilane coupling agent improves the adhesion between the coating layer and the core material, and prevents film abrasion. The additive of the aminosilane coupling agent is preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the silicone resin.

Carrier core materials include iron, magnetite,
Conventionally known materials such as ferrite, copper and glass beads may be used. The particle size is usually 20 to 500 μm, preferably 30 to 1
It is about 00 μm. The resin-coated carrier of the present invention is produced by a method such as spray coating or dip coating as in the conventional case.

A conductive agent is added to the coating layer of the present invention,
The electrical resistance can be reduced, and the edge effect can be mitigated by reducing the electrical resistance.

The conductive agents that can be added are exemplified below. (A) White conductive agent ECT-52 (TiO ₂ system) Titanium Industry Co., Ltd. KV400 (TiO ₂ system) Titanium Industry Co., Ltd. ECR-72 (TiO ₂ system) Titanium Industry Co., Ltd. ECTR-82 (TiO ₂ system) Titanium Industrial Co., Ltd. 500W (TiO ₂ system) Ishihara Sangyo Co., Ltd. 300W (TiO ₂ system) Ishihara Sangyo Co., Ltd. S-1 (TiO ₂ system) Ishihara Sangyo Co., Ltd. W-1 (SnO ₂ system) Mitsubishi Metal Corp. 23K (ZnO) ) Shiromizu Chemical Co., Ltd. Conductive Zinc Flower No. 1 (ZnO) Honjo Chemical Co., Ltd. Conductive Zinc Flower No. 2 (ZnO) Honjo Chemical Co., Ltd. W-10 (TiO ₂ system) Mitsubishi Metal Co., Ltd. Dental WK-100 (conductive fiber) Otsuka Chemical Co., Ltd. Dental WK-200 (conductive fiber) Otsuka Chemical Co., Ltd. Dental WK-300 (conductive fiber) Otsuka Chemical Co., Ltd. MEC300 (SnO ₂ system) Teikoku Kako Co., Ltd. MEC500 (SnO ₂ system) Teikoku Kako Co., Ltd. Ketjen black EC / DJ500 Lion Akzo Ketjen black EC / DJ600 Lion Akzo Denka black Granular Denki Kagaku Denka black Powder Denki Kagaku CONDUCTEX975 Colombia Carbon CONDUCTEX SC Colombia Carbon Made this The particle size of the agent particles 0.01 to 10 [mu] m, more preferably 0.05~2μm are preferred. The amount of the conductive agent added is preferably 0.1 to 85 parts by weight with respect to 100 parts by weight of the silicone resin.

The aminosilane coupling agent of the present invention is
There is also an effect that the conductive agent can be uniformly and quickly dispersed when added. Further, when inexpensive carbon black is used as the conductive agent, the toner becomes cloudy when the carrier coating layer is scraped off when used in combination with a color toner, but in the present invention, the film is It can be said that this is a particularly useful mode because the abrasion can be suppressed as much as possible.

In the present invention, a typical example of the salicylic acid metal salt or the salicylic acid derivative metal salt used as the charge control agent contained in the toner is represented by the following general formula (2).

[Chemical 1] (In the formula, R ¹ , R ² and R ³ are preferably hydrogen or an alkyl group having 1 to 10 carbon atoms or an allyl group. R ¹ , R ² and R ³ may be the same or different at the same time. Is Zn, N
It is any metal selected from i, Co, Pb and Cr. )

The metal salt represented by the general formula is CLAR.
K, J. L. KaO, H (1948) J. Amer. C
It can be easily synthesized by the method described in hem, Soc 70, 2151. For example, zinc is obtained by adding 2 moles of salicylic acid sodium salt (including sodium salt of salicylic acid derivative) and 1 mole of zinc chloride in a solvent, mixing, heating and stirring. The metal salt other than zinc can also be produced according to the above method. The amount of the metal salt in the toner is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the binder resin.

As the binder resin for the toner, all of those which have been used as the binder resin for the toner so far can be applied. Specific examples thereof include homopolymers of styrene such as polystyrene, polychlorostyrene, and polyvinyltoluene and substitution products thereof; styrene-Pchlorostyrene copolymers,
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer,
Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene-acrylonitrile-
Styrene-based copolymers such as indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate , Polyethylene, polypropylene, polyester, polyvinyl butyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorine Examples of the paraffin, paraffin wax and the like may be used alone or in admixture of two or more.

As the toner colorant, all known dyes and pigments can be used. For example, carbon black,
Nigrosine dye, iron black, naphtho-Ruiero-S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow boat, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, R
N, R), Pigment Yellow-L, Benzidine Yellow-
(G, GR), Permanent Yellow (NCG), Palkan Fast Yellow (5G, R), Tartrazine Ray
Ki, quinoline yellow, anthrasan yellow-B
GL, isoindolinone yellow, red iron oxide, red lead, red lead, cadmium red, cadmium mercury red,
Antimon Zhu, Permanent Red 4R, Para Red,
Physe Red, Parachlor Ortho Nitroaniline Red, Lisor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRL)
L, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Litho Red, Leky Red (C, D), Anthocin B, Brilliant Scarlet G, Li Ru Rubin GX, Permanent Red F5R,
Brilliant Carmine 6B, Pigment Scarlet 3
B, Bold-5B, Toluidine Marun, Permanent Bold-F2K, Heliobolide-BL, Bold-10
B, bon maroon light, bon maroon medium, eosin lake, rotamine lake B, rotamine lake Y, alizarin lake, thioindigo red B, thioindigo marine, oil red, oil pink, quina Acridone red, pyrazolen red, polyazo red,
Chrome Million, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Bull, Cerulean Bull, Alkali Bull Lake, Peacock Bull Lake, Victoria Bull Lake, Metal-Free Phthalocyanine Bull -, Phthalocyanine-, fast skible-, indensemble- (RS, BC), indigo,
Ultramarine blue, dark blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, viridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and the like. And the like. The appropriate amount of the colorant used is generally 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.

Further, a conventionally known release agent may be added to the toner. Examples of the release agent include synthetic waxes such as low molecular weight polyethylene and polypropylene, as well as candelilla wax and carnauba wax. , Plant waxes such as rice wax, wood wax, jojoba oil, animal waxes such as beeswax, lanolin, whale wax, mineral waxes such as montan wax and ozokerite, hydrogenated castor oil, hydroxystearic acid, fatty acid amide And oil-based waxes such as phenol fatty acid ester. Further, known fluidizing agents or abrasives may be internally or externally added to the toner particles.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, the part in an Example means a weight part.

Example 1 Toner Example A mixture having the following formulation was heated and kneaded with two roll mills, cooled, pulverized and classified to produce a toner having a particle size of 5 to 20 μm. Polystyrene (Esso D-125) 100 parts Salicylic acid Zn salt (Bontron E84 Orient Chemistry) 2 parts Carbon black (Mitsubishi Kasei # 44) 10 parts

Example of Carrier A coating liquid was prepared as a carrier coating agent according to the following formulation. Silicone resin liquid (Tresil Silicone SR2406, solid content 20%) 500 parts γ- (2-aminoethyl) aminopropyltrimethoxysilane 2.5 parts Toluene 1500 parts For a rotating cylindrical fluidized bed particle coating device. Average particle size 50
5 kg of a ferrite carrier of μ was poured and the coating liquid of the above formulation was sprayed under heating at 80 ° C. while flowing, and the coated product was taken out from the coating device and placed in a constant temperature bath for 2 hours at 200 ° C. A carrier was manufactured by heating and curing the silicon film.

3.0 parts of the toner described above and 100 parts of the carrier are mixed to prepare a negatively charged developer, and the toner is manufactured by F
The image output test at T4420 was good. Also, put the carrier and toner in a ball mill and
Q / after stirring for 0 minutes (corresponding to the start developer)
M (charge amount per unit mass) was −26.0 μc / g. The carrier coating layer is 0.85 at the start.
.mu.m, and the film layer was 0.82 .mu.m and was hardly scraped even after copying 50,000 sheets.

Example 2 Toner Example A mixture having the following formulation was heated and kneaded with two roll mills, cooled, and then pulverized and classified to produce a toner having a particle size of 5 to 20 μm. Polystyrene (Esso D-125) 100 parts Salicylic acid Zn salt (Bontron E84 Orient Chemistry) 2 parts Carbon black (Mitsubishi Kasei # 44) 10 parts

Example of Carrier A coating liquid was prepared as a carrier coating agent according to the following formulation. Silicone resin liquid (Tresil Silicone SR2406, solid content 20%) 500 parts γ- (2-aminoethyl) aminopropyl trimethoxysilane 2.5 parts Conductive carbon (Kettin Black ECDJ600 Lion Akzo Co., Ltd.) ) 3.5 parts Toluene 1500 parts Average particle size 50 in a rotating cylindrical fluidized bed particle coating device
5 kg of a ferrite carrier of μ was poured and the coating liquid of the above formulation was sprayed under heating at 80 ° C. while flowing, and the coated product was taken out from the coating device and placed in a constant temperature bath for 2 hours at 200 ° C. A carrier was manufactured by heating and curing the silicon film.

A negatively charged developer was prepared by mixing 3.0 parts of the toner described above with 100 parts of a carrier, and F-made by Rico-
When an image output test was conducted at T4420, it was good without an edge effect. Q / M of this start developer
Was -23.0 μc / g. The film scraping was similar to the result of Example 1.

Example 3 The same carrier as in Example 1 was manufactured and tested except that the carbon of the carrier coating layer was changed to 60 parts of conductive zinc white NO1 (Honjo Chemical) in Example 2. Similar results to 2 were obtained.

Example 4 Toner Example A mixture of the following color toner formulations was melt-kneaded in a hot roll mill, cooled, coarsely pulverized in a hammer mill, and then finely pulverized in an air-jet pulverizer. The fine powder was classified to have a particle size of 5 to 15 μm to produce each color toner, and 0.5 parts of hydrophobic silica fine powder per 100 parts of toner was added to each color toner.

[Production of Polyester Resin] 7 mol of terephthalic acid, 2 mol of trimellitic acid and 9 mol of polyoxypropylene (2,2) -2,3-bis (4-hydroxyphenyl) propane are condensed by a conventional method. A polyester resin was synthesized.

Yellow toner formulation: Polyester 100 parts Salicylic acid Zn salt (E84, Orient Chemical Co.) 2 parts Yellow pigment (Toyo Ink Mfg. Co., Ltd., Riono-Ruiero-FGN-T) 5 parts

Magenta Toner Formulation: Polyester 100 parts Salicylic acid Zn salt (E84, Orient Chemical Co.) 2 parts Red pigment (Orient Chemical Co., Oil Pink # 312) 5 parts

Ciantona-prescription: 100 parts of the above polyester 2 parts of salicylic acid Zn salt (E84, Orient Chemical Co.) 2 parts of blue pigment (Toyo Ink Mfg. Co., Ltd., Rionolble-FG-7351) 2 parts

Black toner formulation: 100 parts of the above polyester 2 parts of salicylic acid Zn salt (E84, Orient Chemical Co.) 2 parts Carbon black (# 44, Mitsubishi Kasei) 8 parts

Carrier Example A coating liquid for coating a carrier was prepared according to the following formulation. Silicone resin liquid (Torre silicone SR2406, solid content 20%) 500 parts Conductive carbon (Ketchin Black ECDJ600 Lion Akzo Co., Ltd.) 3.5 parts γ- (2-aminoethyl) aminopropyl trimethoxy Silane 2.5 parts Toluene 1500 parts Average particle size 50 in a rotating cylindrical fluidized bed particle coating device
5 kg of a ferrite carrier of μ was poured and the coating liquid of the above formulation was sprayed under heating at 80 ° C. while flowing, and the coated product was taken out from the coating device and placed in a constant temperature bath for 2 hours at 200 ° C. A carrier was manufactured by heating and curing the silicon film.

Toner of each color-4.0 parts and carrier 100
The parts were mixed to prepare four types of negatively charged color developers. The Q / M of the toner was as follows: yellow: -26 µc / g magenta: -24 µc / g cyan: -26 µc / g black: -23 µc / g. These four types of developers are color copying machines (reco
It was set to 8000 Riala) and subjected to an image output test. Also, when the film thickness of each color at the start was 0.85 .mu.m and the carrier coating film after copying 50,000 sheets was checked, it was confirmed that it was 0.80 .mu.m and was hardly scraped, and it was difficult to scrape. Further, no color stain was found on the yellow image.

Comparative Example 1 The same test as in Example 1 was carried out except that the aminosilane in the carrier coating layer was omitted, and the start film thickness was 0.85 μm, and 10,000 sheets were passed. Has been scraped to 0.45 μm. This Q / M was -15 μc / g, which was low in the house.

Comparative Example 2 A copying test was conducted by the same method as in Example 4 except that γ- (2-aminoethyl) aminopropyltrimethoxysilane was removed from the carrier coating layer in Example 4, and a copying test was performed.
It was confirmed that the film thickness after the sheet was 0.45 μm and the film was significantly scraped. Further, when the yellow image after 10,000 sheets was seen, color stains due to the scraping of the carbon of the carrier coating layer were observed, and it was a dull yellow image.

[0034]

As described above, according to the present invention,
By adding an aminosilane coupling agent to the carrier coating layer, the adhesion between the core particles and the silicone resin coating layer is good, the coating layer is prevented from being scraped off, and the salicylic acid metal salt and / or the metal silane coupling agent is adjusted depending on the amount of the aminosilane coupling agent. By freely controlling the charge amount of the toner containing the metal salt of the salicylic acid derivative, the degree of freedom in designing the toner formulation can be increased. In addition, when a conductive substance is dispersed in the carrier coating layer, the dispersibility can be improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takahisa Kato 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Tomomi Suzuki Inc. 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Within Ricoh Company (72) Inventor Hiroaki Matsuda 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Company, Ltd.

Claims (2)

[Claims] 1. A two-component developer comprising a carrier and a toner, carrier particles having a coating layer comprising a silicone resin and an aminosilane coupling agent as main components on the surface, a salicylic acid metal salt and // as a charge control agent. Alternatively, a dry two-component developer comprising toner particles containing a metal salt of a salicylic acid derivative. 2. The dry two-component developer according to claim 1, wherein a conductive substance is dispersed in the coating layer on the surface of the carrier.