JPH04218063A - Toner - Google Patents

Abstract

PURPOSE:To provide the toner degradable under the ground when the toner fixed to a transfer paper is used up and buried as waste. CONSTITUTION:The toner comprises at least a binder resin, an electric charge controller, and biodegradable plastic or the toner comprising at least a binder resin, a colorant a charge controller, and biodegradable plastic and photo- degradable plastic.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing electrostatic latent images.

2. Description of the Related Art A toner for developing an electrostatic latent image consists of a main binder resin, a colorant, a polarity control agent, a fluidity improver, and the like. The main component is plastic, and as the production and consumption of plastic has increased in recent years, the amount of waste generated has also been increasing year by year. The disadvantage of this plastic is that used plastic does not decompose in nature.

[0002] Therefore, this plastic waste accumulates on the earth, causing various problems. For example, when garbage containing plastic is incinerated, it releases a high amount of energy, which damages the incinerator. Additionally, CO2 generated during incineration poses a problem in global warming. If this plastic waste is disposed of in a landfill, it will not rot permanently, and if it is a bulky item like Styrofoam, the ground will not solidify. In order to deal with these problems, it has been proposed to use collapsible plastics in toners as well (Japanese Patent Application Laid-open Nos. 122655/1980 and 55940/1987).

0003

[Problems to be Solved by the Invention] However, the above-mentioned disintegration is due to photodecomposition, and it is not effective when disposed of in a landfill underground. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a toner that can decompose the toner adhered to paper even if the copied paper is disposed of in a landfill.

0004

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventor found that it is effective to use biodegradable plastics in toner, and arrived at the present invention. That is, the present invention provides: (1) a toner containing at least a binder resin, a colorant, a charge control agent, and a biodegradable plastic;
2) A toner containing at least a binder resin, a colorant, a charge control agent, a biodegradable plastic, and a photodegradant. The following points should generally be taken into account when using materials for toner for developing electrostatic latent images.

(1) As for electrical properties, the charging (Q/M) should be stable, and the resistance and dielectricity of the toner should be appropriate. (2) Good fluidity for smooth toner replenishment. (3) As for thermal characteristics, toner is difficult to adhere to the fixing roller and toner is easy to adhere to paper. (4) The toner must be stable during storage. (5) As for safety, there is no toxicity. etc., you must be careful.

The biodegradable plastic used in the present invention satisfies all of the above requirements. Biodegradable plastics include natural plastics and synthetic plastics, and both can be used in the toner of the present invention. Representative examples of natural plastics include polysaccharides such as oxidized cellulose, mucopolysaccharides, chitin, and starch; natural polyesters such as polyhydroxybutyric acid and its derivatives, and malic acid polymers; natural polypeptides, etc. . Commercial products of polysaccharides include ECOSTAR and ECOSTAR Plus (both trade names of Hagiwara Kogyo Co., Ltd.), and examples of polyhydroxybutyric acid and its derivatives include poly3-hydroxybutyrate, There are 3-hydroxybutyrate/3-hydroxyvalerate copolymers, 3-hydroxybutyrate/4-hydroxybutyrate copolymers, etc. Commercially available products include, for example, Biopol.
, ICI's product name).

Typical examples of synthetic plastics include synthetic polypeptides; synthetic polyesters such as polylactone, polylactide, and glycolide; polyphosphazenes;
Examples include polycyanoacrylates; polyacid anhydrides. Examples of polypeptides include ε-caprolactam, polycaprolactam, aliphatic amino acids, amino acids having an aromatic nucleus, and amino acids having a heterocycle. Examples of polylactone include polycaprolactone, polyethylene adipate, polytetramethylene adipate, polypropiolactone, and a copolymer of polycaprolactone and polyesteramide.
ne, trade name of Union Carbide Company). Examples of phosphazenes include hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and commercially available products include PR-1000 (trade name of Nippon Soda Co., Ltd.) and Ipel F (trade name of Ethyl Corporation).

The toner of the present invention comprises at least a binder resin, a colorant, a charge control agent, and a biodegradable plastic. As the binder resin, polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene - Vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer) , styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-methyl chloroacrylate copolymer, styrene-acrolinitrile-acrylic acid ester copolymer, etc. (monopolymers or copolymers containing substituents), vinyl chloride resin, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resin, polyurethane resin, ketone resin, ethylene - Ethyl acrylate copolymer, xylene resin, polyvinyl butyral, and styrene resin is particularly preferably used.

Specific examples of colorants for black include carbon black, spirit black, and aniline black (C.I. Pigment Black).
1) etc. Specific examples of yellow colorants include C.I. I. Pigment Yellow
1 Simuler Fast Yellow G
H (Dainippon Ink)C. I. Pigment Y
yellow 3 Simuler Fast Yel
low 10GH (Dainippon Ink) C. I. Pi
gment Yellow 12 Symuler F
ast Yellow GF (Dainippon Ink) C.
I. Pigment Yellow 13 Symu
ler Fast Yellow GRF (Dainippon Ink) C. I. Pigment Yellow 1
4 Simuler Fast Yellow 5GR
(Dainippon Ink) C. I. Pigment Ye
low 17 Simuler Fast Yellow
ow 8GR (Dainippon Ink)

Furthermore, C
．． I. Pigment Yellow 12 as Yellow 152 (Arimoto Chemical) Pigment Yellow GRT (Sanyo Dyes) Sumika Print Yellow ST-O (Sumitomo Chemical) Benzine Yellow 1316 (Noma Chemical) Seika Fast Yellow 2
300 (Dainichiseika) Lionor Yellow GRT
(Toyo Ink)

[0011] etc. can be mentioned. Specific examples of magenta colorants include C.I. I. Pigment Red 81 Symu
lex Rhodamine Y Toner F
(Dainippon Ink)C. I. Pigment Red
122 Permanent Pink E (Hoechst) C. I. Pigment Red 57S
ymuler Brill Carmine 6B
(Dainippon Ink)C. I. Pigment Red
22 Simuler Fast Bril Sca
rlet BG (Dainippon Ink) C. I. Pig
ment Red 21 Sanyo Fast R
ed GR (Sanyo Color) C. I. Pigment
Red 18 Sanyo Toluidine
Maroon Medium (Sanyo Color) C. I.
Pigment Red 114 Symuler
Fast Carmine B5 (Dainippon Ink)
C. I. Pigment Red 112 Symu
ler Fast Red FGR (Dainippon Ink) C. I. Pigment Red 5 Sym
uler Fast Carmine FB (Dainippon Ink) and the like.

Specific examples of cyan colorants include C.I. I.
Pigment Blue 15 Fastogen
Blue GS (Dainippon Ink) C. I. Pi
gment Blue 15 Fastogen Bl
ue GS Chromofine SR (Dainichiseika) C. I. Pigment Blue 16 Sum
itone Cyanine Blue LG (Sumitomo Chemical) C. I. Pigment Green 7
Phthalocyanine Green (Tokyo Ink) C. I. Pigment Green 36
Cyanine Green 2YL (Toyo Ink) C. I. Pigment Blue 15:3
Examples include Cyanine Blue GGK (Nippon Pigment). The colorant is added in an amount of 0.5 to 40 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts of the binder resin.
Used at 30 parts by weight. As charge control agents, those with negative polarity include metal complex dyes, metal salts of salicylic acid, or metal salts of salicylic acid derivatives, and those with positive polarity include nigrosine dyes, quaternary ammonium salts, and resins containing amino groups. etc. This charge control agent is a binder resin 1
0.05 to 25 parts by weight, preferably 0.00 parts.
It is used in an amount of 1 to 20 parts by weight.

[0013] Furthermore, the biodegradable plastic used in the present invention is one that is decomposed into CO2 and water by microorganisms and enzymes in the soil, and materials classified as polysaccharides are particularly preferable, and the amount of this plastic is determined by the amount of biodegradable plastic. It is used in an amount of 1 to 70 parts by weight, preferably 1.5 to 50 parts by weight, based on 100 parts of the binder resin. Further, in the present invention, the natural decomposition of the toner can be improved by further including a resin photodegrading agent. Examples of the photodecomposition agent include ketone type such as polyvinyl ketone, ethylene/carbon monoxide type, and accelerator type. In addition, many proposals have been made to date, such as JP-A-57
-55940 and 59-133234 are known. The use as a binder for toner has also been proposed in JP-A-61-122655. In the present invention, the degradability can be improved by using the above photodegrading agent in combination, and the total amount including the biodegradable plastic is 1 to 70 parts by weight based on 100 parts by weight of the binder resin. . The mixing ratio of the biodegradable plastic and the photodegradant may be any desired ratio, but is preferably 1:1 to 1:1.
It is 4.

The toner particle size of the present invention is about 30 μm or less,
Preferably it is 3 to 20 μm. In addition, a toner property modifier may be added to the toner or to the surface of the toner. For example, TiO2 is used to improve toner fluidity.
, SiO2, SnO2, Al2O3, and other external additives may be added. Examples of carriers used in the present invention include iron oxide powder, Ni-Zn ferrite, Gu-Zn ferrite, Ba ferrite, Sr ferrite, ZnO ferrite, glass beads, iron powder, Ni powder, Co powder, resin beads, etc. Those having a particle size of ~300 μm are used. The thickness is preferably 15 to 150 μm, and a coating layer may be provided if necessary.

Next, as the mold release resin for carrier coating, polyolefin resins such as polyethylene,
polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resins (e.g. polymethyl methacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, Polyvinyl ether and polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; silicone resins such as straight silicone resins consisting of organosiloxane bonds or modified products thereof (e.g. alkyd resins, polyesters, epoxy resins, Products modified with polyurethane, etc.); Fluororesins such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride,
Polymers or copolymers such as polychlorotrifluoroethylene; polyamides; polyesters, such as polyethylene terephthalate; polyurethanes; polycarbonates; amino resins, such as urea-formaldehyde resins; and epoxy resins. Among them, acrylic resins, silicone resins or modified products thereof, and fluororesins, particularly silicone resins or modified products thereof, are preferred from the viewpoint of preventing the spent toner from adhering to the carrier. A commercially available silicone resin (straight silicone resin) is KR2 manufactured by Shin-Etsu Chemical Co., Ltd.
71, KR255, KR251, SR2400, SR2406 manufactured by Toray Silicone Co., Ltd., and modified silicone resins such as KR206 (alkyd resin modified product), KR3093 (acrylic resin modified product), and ES1001N (epoxy resin modified product) manufactured by Shin-Etsu Chemical Co., Ltd. , Toray Silicone SR2115 (epoxy resin modified product),
Examples include SR2110 (alkyd resin modified product).

[0016] The appropriate amount of the above-mentioned releasable resin to be used is about 0.5 to 50 parts by weight per 100 parts by weight of the carrier core material. The present toner may be used as one component, and therefore may contain magnetic powder. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used, and includes powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of this magnetic powder is 15 to 70% by weight based on the weight of the toner.

[0017]

[Examples] The present invention will be explained in more detail with reference to Examples below. Example 1 Average particle diameter of approximately 100μ as carrier for two-component developer
m steel beads (Microshot SF-100, manufactured by Shinto Brater) were prepared. Further, a mixture of the following formulation was kneaded under heating on two rolls, cooled, and then crushed and classified to produce a toner for a two-component developer having a particle size of 5 to 20 μm. Polystyrene (Esso D-125)
100 parts Metal-containing dye (Hodogaya Chemical Co., Ltd. Spiron Black BH) 5 parts
Carbon black (Mitsubishi Kasei #44)
10 parts Biodegradable plastic (Ecostar Hagiwara Industries) 13 parts

A two-component developer was prepared by mixing 100 parts of these carriers and 3.0 parts of toner. In addition, the amount of charge (Q/M) of the toner in this developer by the blow-off method is -16μ
c/g. When this agent was imaged using an FT6650 (manufactured by Ricoh) copying machine, an image exactly the same as the conventional one was obtained. Since this toner contains biodegradable plastic, not only the paper but also the toner can be broken down into crumbly particles after the copy paper is discarded. Using the developer, a solid image of the toner was formed on the entire surface of copy paper using a commercially available electrophotographic copying machine.
00 (Ricoh paper)], the copy paper was buried in the soil for 4 months, and then the copy paper was taken out and 2
When I tried to bend it, a crack appeared on the toner surface. or,
When I rolled up a large piece of copy paper and rubbed the toner sides together, I noticed that the toner had loosened up into fine particles that looked like they had been crushed. As mentioned above, the strength of the toner clearly deteriorated due to decomposition. Immediately after copying, there were no cracks on the toner surface even after bending, and no loosening occurred even after rubbing.

Example 2 The carrier in Example 1 was changed to the following (coated carrier)
. A coating liquid was prepared as a carrier coating material according to the following formulation. Silicone resin liquid (Toray Silicone SR2406
, solid content 20%) 500 parts by weight Toluene

1500 parts by weight rotating disk type fluidized bed particle coating equipment with an average particle size of 50
Put 5 kg of μ ferrite carrier, spread the coating liquid of the above formulation while heating it at 80℃, and take out the coated material from the coating equipment, put it in a constant temperature bath, heat it at 200℃ for 2 hours, and apply silicone. The film was allowed to cure. The toner was the same as in Example 1, and the test results were the same as in Example 1.

Example 3 Carrier Example A coating liquid was prepared as a carrier coating material according to the following formulation. Silicone resin liquid (Toray Silicone SR2406
, solid content 20%) 500 parts by weight Toluene

1500 parts by weight rotating disk type fluidized bed particle coating equipment with an average particle size of 50
Put 5 kg of μ ferrite carrier, spread the coating liquid of the above formulation while heating it at 80℃, and take out the coated material from the coating equipment, put it in a constant temperature bath, heat it at 200℃ for 2 hours, and apply silicone. The film was allowed to cure. Toner Example A mixture of the following formulation was kneaded on two rolls under heating, cooled, and then crushed and classified to obtain a particle size of 5 to 20 μm.
A toner for a two-component developer was prepared. Polystyrene (Esso D-125)
100 parts Dye (Orient Chemical Co., Ltd. Special Black SB) 5
Carbon black (Mitsubishi Kasei #44)
Part 10 Ecostar (manufactured by Hagiwara Kogyo)
Part 13

A two-component developer was prepared by mixing 100 parts of these carriers and 3.0 parts of toner. The toner charge amount (Q/M) of this developer by the blow-off method was +16 μc/g. When this agent was imaged using an FT4460 (manufactured by Ricoh) copying machine, an image exactly the same as the conventional one was obtained. Since this toner contains biodegradable plastic, not only the paper but also the toner can be broken down into crumbly particles after the copy paper is discarded. The test results were the same as in Example 1. Example 4 (color toner example) Carrier example: Example 2 Toner example: Only the coloring material in Example 1 was changed as follows. The coloring materials in the toner formulation were the color toners shown in Table 1.

[0022]

[Table 1]

A mixture of the following formulation was kneaded under heat on two rolls, cooled, and then pulverized and classified to produce a toner for a two-component developer having a particle size of 5 to 20 μm. Polystyrene (Esso D-125) 10
0 parts Charge control agent: Quaternary ammonium salt 2
Part coloring material: (See Table-1
Part) Ecostar (manufactured by Hagiwara Kogyo Co., Ltd.)
13 parts 100 parts of these carriers and 3 parts of each toner
．． A two-component developer was prepared by mixing 0 parts. In addition,
The charge amount (Q/M) of each toner in this developer by the blow-off method was +16 μc/g. When images were produced using these three color agents using an ARTAGE 5330 (manufactured by Ricoh) copying machine, images exactly the same as those of the prior art were obtained. This toner contains biodegradable plastic, so after the copy paper is discarded, not only the paper but also the toner can be broken down into crumbly particles. The test results were the same as in Example 1.

Example 5 A toner was prepared by replacing the binder resin (polystyrene) in Example 1 with a polyester resin (Atrac 382A manufactured by Kao) and treated in the same manner as in Example 1, resulting in the same results as in Example 1. Got the results. Example 6 (Example of one-component toner) A mixture of the following formulation was kneaded under heat on two rolls, cooled, and then pulverized and classified to produce a toner for a two-component developer having a particle size of 5 to 20 μm. Polystyrene (Esso D-125) 10
0 parts dye (Special Black SB manufactured by Orient Chemical Co., Ltd.) 5 parts Ecostar (manufactured by Hagiwara Kogyo Co., Ltd.) 13 parts Magnetic material
50 copies

[0025] This toner is MYR.
When an image was produced using an ICOPY M5 (manufactured by Ricoh) copying machine, an image exactly the same as the conventional one was obtained. This toner contains biodegradable plastic, so after the copy paper is discarded, not only the paper but also the toner can be broken down into crumbly particles. The test results were the same as in Example 1. Example 7 In Example 1, the amount of biodegradable plastic was changed to 8 parts, and 5 parts of methyl vinyl ketone/styrene copolymer was added as a photodegrading agent to prepare a toner, and the same procedure as in Example 1 was carried out. When an outdoor decomposition test was conducted, degradability comparable to that of Example 1 was obtained after 3 months.

Example 8 In Example 1, a toner was prepared by replacing the biodegradable plastic with the following substances. (1) 3-hydroxybutyrate/3-hydroxyvalerate copolymer (2) polycaprolactam (3) polyglycolide (4) polycaprolactone (5) 5 types of toners, including hexachlorocyclotriphosphazene - was subjected to an outdoor decomposition test in the same manner as in Example 1, and the same level of decomposition as in Example 1 was obtained after 4 months.

Comparative Example A toner was prepared by removing Ecostar (biodegradable plastic) from the toner of Example 1, but since this toner is exactly the same as the conventional toner, the toner cannot be broken down into crumbly fine particles. In addition, in the same way as in Example 1, in the test of the copy paper after putting the copy paper in soil and the test of the copy paper immediately after copying, no cracks were observed on the toner surface, and no loosening of the toner was observed even when rubbed together. Ta.

[0028]

[Effects of the Invention] As explained above, by including biodegradable plastic in toner, even if the copy paper containing this toner is disposed of as waste, the effect of the biodegradable plastic in the toner is still high. The toner can be broken down into crumbly particles, causing no environmental problems on earth.

Claims (2)

[Claims] 1. A toner containing at least a binder resin, a colorant, a charge control agent, and a biodegradable plastic. 2. A toner containing at least a binder resin, a colorant, a charge control agent, a biodegradable plastic, and a photodegradant.