JPH1152612A - Toner binder resin and toner using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide binder resin used for low temperature fixing type toner that can obtain an image excellent in color reproducibility and image density of intermediate gradation by containing specific petroleum resin. SOLUTION: This toner binder resin contains petroleum resin with Gardner color scale of 10 or less. Petroleum resin used for the toner binder resin is not particularly limited, but aliphatic petroleum resin, aromatic petroleum resin, cyclopentadiene group petroleum resin and the like are used. In case of Gardner color scale exceeding 10, toner excellent in color reproducibility and image density of intermediate gradation cannot be obtained. It is therefore desirable that the Gardner color scale of petroleum resin is 5 or less, particularly 2 or less. This toner resin contains one or two kinds of binder resin. The content of binder resin in the toner resin is not particularly limited, but it is normally 1 wt.% or more, desirably 70 wt.% or more. In case of 70 wt.% or more, grindability at the time of manufacturing toner is particularly excellent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner bander resin and an electrophotographic toner using the same.
For more details, see electrophotographic copiers, printers,
The present invention relates to a binder resin which is used for facsimile and the like and which provides a toner capable of obtaining an image with excellent image density and color reproducibility of intermediate gradations, and a toner having the above-mentioned performance using the binder resin.

[0002]

2. Description of the Related Art Toners widely used in electrophotographic copiers, printers, facsimile machines, etc. are based on electrical properties such as triboelectric charging and electric resistance related to development and transfer performance, and fixing performance and heat resistance performance. Regarding thermal properties related to storage stability) and powder properties such as fluidity and hardness, appropriate control according to the usage level is required. Regarding the color of the toner, a binder resin which does not impair the color tone of the colorant, such as color reproducibility and image density of intermediate gradation, is desired not only for color but also for monochrome. Conventionally, as a toner binder resin, for example, styrene acrylic resin, polyester resin, epoxy resin and the like have been widely used. In recent years, from the viewpoint of energy saving, low-temperature fixing type toner has been actively developed and softened. Attention has been focused on petroleum resins that are effective in lowering the temperature. However, a toner containing this petroleum resin as a toner resin has drawbacks such as impairing the hue of the colorant in color applications and difficulty in controlling the image density of intermediate gradations even in monochrome applications.

[0003]

SUMMARY OF THE INVENTION The present invention provides a binder resin which provides a toner which is of a low-temperature fixing type and which is capable of obtaining an image having excellent image density and color reproducibility of a middle gradation under such circumstances. It is another object of the present invention to provide a toner having the above-mentioned performance using the binder resin.

[0004]

Means for Solving the Problems As a result of extensive studies to achieve the above object, the present inventors have found that a petroleum resin having a Gardner color number equal to or less than a specific value is suitable for the purpose as a toner binder resin. I found out what could be done. The present invention has been completed based on such findings. That is, the present invention provides an electrophotographic toner binder resin containing a petroleum resin having a Gardner color number of 10 or less. The present invention also provides an electrophotographic toner comprising the above binder resin as a toner resin.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The petroleum resin used in the toner binder resin of the present invention is not particularly limited, and any one of various conventionally known resins can be selected and used. As the petroleum resin, for example, aliphatic petroleum resin, aromatic petroleum resin, cyclopentadiene petroleum resin, alicyclic aliphatic petroleum resin, or two or more kinds of monomers constituting each of these resins are appropriately selected and polymerized. And a copolymer resin obtained by polymerizing the above-mentioned monomer and another polymerizable monomer, and furthermore, a part of a carbon-carbon unsaturated bond and / or an aromatic ring of these resins. Alternatively, a resin obtained by hydrogenating all of them may be used.

The aliphatic petroleum resin includes, for example, C4 to C4 having a boiling point of -10 to 100 ° C among naphtha cracked oils.
Polymerizable components contained in 6 fractions, specifically C4 fraction: 1
2-butene; isobutene; 1,3-butadiene; C5 cut: 1-pentene; 2-pentene; 2-methyl-1-butene; 3-methyl-1-butene; 2-methyl-2-butene (Isoprene); 1,3-pentadiene;
Cyclopentene; cyclopentadiene; 2-methyl-
1,3-butadiene, C6 cut: 1-hexene; 2-hexene; 3-hexene; 4-methyl-1-pentene;
-Methyl-2-pentene; 2-methyl-2-pentene;
2-methyl-1-pentene; 3-methyl-2-pentene; 2-ethyl-1-butene; 2,3-dimethyl-1-
2,3-dimethyl-2-butene; 2,2-dimethyl-1-butene; 1,3-hexadiene; 1,4-hexadiene; 2-methyl-1,4-pentadiene;
1,4-hexadiene; 2,4-hexadiene; 2-methyl-1,3-pentadiene; 3-methyl-1,3-pentadiene; 4-methyl-1,3-pentadiene; Cyclohexene; 1,3
-Cyclohexadiene; 1,4-cyclohexadiene;
Resins obtained by polymerizing at least one selected from 1-methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, and the like can be given.

The aromatic petroleum resin is, for example, an aromatic vinyl monomer mainly composed of a C8 to C10 fraction in naphtha cracked oil, for example, styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, Resins obtained by polymerizing at least one selected from alkyl-substituted indene, allylbenzene, allyltoluene, tert-butyltoluene, tert-butylallylbenzene and the like can be mentioned. Examples of the cyclopentadiene-based petroleum resin and the alicyclic aliphatic-based petroleum resin include, for example, a naphtha cracked oil having a boiling point of -10 to 50C.
A resin obtained by polymerizing at least one selected from aliphatic cyclic unsaturated hydrocarbon monomers obtained by cyclizing and dimerizing a diene or olefin contained in the fraction of the diene by an Diels-Alder reaction. it can. For the polymerization of the monomer, any method of cationic polymerization, radical polymerization, thermal polymerization, anionic polymerization, ionic coordination polymerization, suspension polymerization, emulsion polymerization, and polymerization using a transition metal complex can be used. There is no particular limitation on the method of hydrogenation,
A conventionally known method can be used.

Among these resins, in particular, styrene-dicyclopentadiene copolymer (styrene unit / dicyclopentadiene unit weight ratio = 90 / 10-0 / 100), indene-dicyclopentadiene copolymer, indene −
Styrene-dicyclopentadiene copolymers (indenes: indene, methylindene, etc., styrenes: styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, dicyclopentadienes: dicyclopentadiene, dihydrodicyclo Pentadiene), dicyclopentadiene polymers, and resins obtained by hydrogenating some or all of carbon-carbon unsaturated bonds and aromatic rings of these resins. Other specific examples of petroleum resins include (1) the boiling point of naphtha cracked oil,
(2) cyclization and dimerization of the olefins and / or dienes contained in the naphtha-cracked oil in the fraction having a boiling point of -10 to 50 ° C by the Diels-Alder reaction An aliphatic cyclic unsaturated hydrocarbon monomer, (3) a chain olefin having 3 to 10 carbon atoms,
(4) Norbornene-based monomers (2-norbornene, 5
-Vinyl norbornene, 2-vinyl norbornane, 2-
(5) ethylidene norbornane, 2-isopropenyl norbornane, 2-isopropylidene norbornane, etc.
At least one monomer selected from mono- or diolefins having 4 to 6 carbon atoms and (6) conjugated diolefins having 4 to 5 carbon atoms is an essential component, and styrene,
Resin obtained by copolymerizing at least one selected from α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, alkyl-substituted indene, cyclopentadiene, dicyclopentadiene and other polymerizable monomers, and these resins Preferably, a resin obtained by hydrogenating a part or all of a carbon-carbon unsaturated bond or an aromatic ring is preferably used.

Examples of the other polymerizable monomers include known monomers such as chain olefins having 2 to 20 carbon atoms such as ethylene, propylene, octene and dodecene, cyclic olefins having 7 to 20 carbon atoms such as pinene, limonene, and the like. Polyenes having 6 to 20 carbon atoms such as myrcene; (meth) acrylates such as methyl, ethyl, butyl, octyl, phenyl, and saturyl esters of (meth) acrylic acid; vinyl chloride; vinylidene chloride; -Dichloroethylene; trichloroethylene; tetrachloroethylene; vinyl fluoride; vinylidene fluoride; 1,2-difluoroethylene; trifluoroethylene; tetrafluoroethylene; vinyl halides such as vinyl bromide, vinyl silanes such as trialkyl vinyl silane and trialkoxy vinyl silane. , Methyl vinyl ketone, vinyl silanes such as vinyl silane, α, β-unsaturated ketones such as methyl vinyl ketone and phenyl vinyl ketone, and acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, maleic acid, maleic acid ester, and anhydride Maleic acid, cyclopropane and its derivatives, cyclobutane and its derivatives, oxetane and its derivatives, tetrahydrofuran and its derivatives, acetylene and its derivatives,
α, β-unsaturated aldehyde, α, β-unsaturated ester,
Examples thereof include dithiols having 2 to 10 carbon atoms.

The naphtha cracked oil has a boiling point of -10 to 8
The monomers contained in the 0 ° C. fraction include C4 to C6
And the polymerizable component is, for example, C4: 1-butene; 2-butene; isobutene; 1,3-butadiene, C5: 1-pentene; 2-pentene; 2-methyl -1-butene; 3-methyl-1-butene; 2-methyl-2-butene (isoprene);
-Pentadiene; cyclopentene; cyclopentadiene; 2-methyl-1,3-butadiene, C6: 1-hexene; 2-hexene; 3-hexene;
Pentene; 4-methyl-2-pentene; 2-methyl-2
-Pentene; 2-methyl-1-pentene; 3-methyl-
2-pentene; 2-ethyl-1-butene; 2,3-dimethyl-1-butene; 2,3-dimethyl-2-butene;
2,2-dimethyl-1-butene; 1,3-hexadiene; 1,4-hexadiene; 2-methyl-1,4-pentadiene; 3-methyl-1,4-pentadiene; 1,5
-Hexadiene; 2,4-hexadiene; 2-methyl-
1,3-pentadiene; 3-methyl-1,3-pentadiene; 4-methyl-1,3-pentadiene; cyclohexene; 1,3-cyclohexadiene; 1,4-cyclohexadiene; 1-methylcyclopentene; 3-methyl Cyclopentene; 4-methylcyclopentene;

The petroleum resin used in the toner binder resin of the present invention has a Gardner color number (JIS K690).
(Measured in accordance with No. 1) must be 10 or less. When the number of colors exceeds 10, a toner excellent in image density and color reproducibility of intermediate gradation cannot be obtained, and the effect of the present invention cannot be exhibited. In order to sufficiently exhibit the effects of the present invention, the petroleum resin preferably has a Gardner color number of 5 or less, and particularly preferably 2 or less. Next, the electrophotographic toner of the present invention will be described. The toner of the present invention contains one or more of the binder resins of the present invention as the toner resin, and the content of the binder resin of the present invention in the toner resin is not particularly limited. % By weight or more, preferably 70% by weight or more. When the content of the binder resin is 70% by weight or more, the pulverizability during the production of the toner is particularly good. If the content of the binder resin is less than 1% by weight, the effects of the present invention may not be sufficiently exhibited.

In the toner of the present invention, an elastomer can be used together with the binder resin of the present invention as the toner resin. By using this elastomer together, the rheological properties at the time of melting are improved, and the offset occurrence temperature is increased. The elastomer is not particularly limited, and any elastomer can be selected from conventionally known elastomers. Examples of the elastomer include nitrile rubber, ethylene propylene rubber, chloroprene rubber, silicone rubber, fluorine rubber, ethylene acrylic rubber, polyester elastomer, epichlorohydrin rubber, acrylic rubber, liquid rubber, chlorinated polyethylene,
Butadiene rubber, styrene-butadiene copolymer, natural rubber, 1,2-polybutadiene, butyl rubber, chlorosulfonated polyethylene, polysulfide rubber, urethane rubber, styrene-based TPE (thermoplastic elastomer), olefin-based TPE, urethane-based TPE, Ester-based TPE, polyvinyl chloride-based TPE, butyl rubber-grafted polyethylene, trans 1,4-polyisoprene ionomer, natural rubber-based TPE, and the like are applicable. Especially styrene
Butadiene copolymers are preferred.

These elastomers may be used alone or in combination of two or more. When the binder resin of the present invention and the above elastomer are used in combination, the content of the elastomer in the total toner resin is 3%.
It is preferably 0% by weight or less. If this content exceeds 30% by weight, the pulverizability during the production of the toner may be reduced.
Further, in the toner of the present invention, as the toner resin,
A wax can be used together with the binder resin of the present invention. By using this wax in combination, tack resistance is improved, and the softening point (Tm) can be greatly reduced without substantially lowering the glass transition temperature (Tg).
The wax is not particularly limited, and any wax can be selected from conventionally known waxes. Examples of the wax include animal and vegetable waxes, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, polyethylene oxide wax, polypropylene wax, and polypropylene oxide. Wax, higher fatty acid wax, higher fatty acid ester wax, carnauba wax, Fischer-Tropsch wax and the like are preferably used. Among them, Fischer-Tropsch wax is particularly preferred. These waxes may be used alone or in combination of two or more. When the binder resin of the present invention and the wax are used in combination, the content of the wax in the total toner resin is preferably 30% by weight or less. If the content exceeds 30% by weight, Tg may be reduced, and blocking resistance may be deteriorated. Further, the wax can be used in combination with the elastomer.

[0014] In addition, as long as the effects of the present invention are not impaired,
If desired, a conventionally known thermoplastic resin can be used in combination. Examples of the conventionally known thermoplastic resin include polyester resins (alcohol components: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, bisphenol A-ethylene glycol modified) Diol, 1,3-
Α, ω-alkylene diols such as propylene glycol (C2 to C12), hydrogenated bisphenol A, bisphenol F, bisphenol F-ethylene glycol modified diol, bisphenol S, bisphenol S-ethylene glycol modified diol, biphenol, biphenol-ethylene glycol modified Diol, neopentyglycol, trihydric or higher polyhydric alcohol, carboxylic acid:
Aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, trivalent or higher polycarboxylic acid), polystyrene, styrene oligomer, amorphous poly-α-olefin, chloropolystyrene, poly-α-methylstyrene,
Poly-4-methoxystyrene, poly-4-hydroxystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyl chloride copolymer, styrene-maleic acid copolymer, styrene-vinyl acetate copolymer Polymers, styrene-acrylate copolymers (methyl, ethyl, butyl, octyl, phenyl ester), styrene-methacrylate copolymers (methyl, ethyl, butyl, octyl, phenyl ester),
Styrene-α-methyl methyl acrylate copolymer, styrene-acrylonitrile-acrylate copolymer, α-methylstyrene-acrylate copolymer (methyl, ethyl, butyl, octyl, phenyl ester), α-methyl Styrene-methacrylic ester copolymer (methyl, ethyl, butyl, octyl, phenyl ester), α-methylstyrene-α-chloromethyl acrylate copolymer, α-methylstyrene-acrylonitrile-acrylic acid ester copolymer Coalescence, vinyl chloride resin,
Rosin-modified maleic resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, and the like. One of these thermoplastic resins may be used, or two or more of them may be used in combination.

If necessary, a conventionally known antioxidant may be added to the toner of the present invention or the toner resin used therein, as long as the effects of the present invention are not impaired. As the conventionally known antioxidants, hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, sulfide antioxidants, organic phosphorus antioxidants, and the like can be applied. Among them, hindered phenolic antioxidants are preferred. This antioxidant may be used alone or in combination of two or more. Further, other additives such as an antioxidant, an antiozonant, an ultraviolet absorber, a light stabilizer, and the like may be added to the toner of the present invention or the toner resin used therein, as long as the effects of the present invention are not impaired. Softener, reinforcing agent, filler, mastication accelerator, foaming agent, foaming aid, lubricant, internal mold release agent, flame retardant, kneading antistatic agent, coloring agent, coupling agent,
Preservatives, flavoring agents and the like may be added.

The toner for electrophotography according to the present invention usually comprises 25 to 95% by weight of a toner binder (toner resin), 0 to 10% by weight of a colorant, 0 to 70% by weight of a magnetic powder, and 0 of a charge control agent.
And 10 to 10% by weight of a lubricant, and 0 to 1.5% by weight of a fluidizing agent and 0 to 1.5% of a cleaning aid as external additives. Examples of the coloring agent include conventionally known organic or inorganic coloring agents such as carbon black, copper oxide, manganese dioxide, alinine black, activated carbon, nonmagnetic ferrite, magnetic ferrite, magnetite, iron black, benzidine yellow, disazo yellow. Quinacdrine, naphthol azo pigments, quinacridone, rhodamine B, phthalocyanine, titanium white, zinc white, and the like. In the magnetic toner, when the magnetic powder itself is colored (black), the use of the coloring agent is not essential. Examples of the magnetic powder include conventionally known magnetic powders such as iron, cobalt, nickel, magnetite, hematite, and ferrite. The particle size of the magnetic powder is usually 0.05 to 1 μm, preferably 0.1 to 0.5 μm.
m.

Further, the charge control agent is a substance capable of giving a positive or negative charge by triboelectric charging. Examples of such a substance include Nigrosine Base EX (manufactured by Orient Chemical Industries) and P-51 (Orient Chemical Co., Ltd.). Chemical Industry)
Copy charge PXVP435 [manufactured by Hoechst Co., Ltd.],
Alkoxylated amine, alkyl amide, molybdic acid chelate pigment, PLZ1001 (manufactured by Shikoku Kasei Kogyo), Bontron S-22 (manufactured by Orient Chemical Industries), Bontron S-34 (manufactured by Orient Chemical Industries), Bontron E-81 ( Orient Chemical Industries), Bontron E-
84 (manufactured by Orient Chemical Industries), Spiron Black T
RH (manufactured by Hodogaya Chemical Industries), thioindigo pigments,
Copy Charge NXVP434, Bontron E-89
(Manufactured by Orient Chemical Co., Ltd.), magnesium fluoride, carbon fluoride, metal oxycarboxylate complex, metal dicarboxylate complex, metal complex of amino acid, metal complex of diketone, metal complex of diamine, benzene-benzene derivative skeleton containing azo group metal complex, Azo group-containing benzene-naphthalene derivative skeleton metal complex, benzyldimethyl-hexadecylammonium chloride, desilyltrimethylammonium chloride, metal complex, nigrosine base, nigrosine hydrochloride, safranin, crystal violet,
Various conventionally known compounds such as a quaternary ammonium salt, an alkylsalicylate metal complex, a calixarene-based compound, a boron compound, a fluorinated quaternary ammonium salt, an azo-based metal complex, a triphenylmethane-based dye, and dibutyltin oxide are applicable. .

Examples of the lubricant include conventionally known lubricants such as, for example, polytetrafluoroethylene, low molecular weight polyolefin, fatty acids and their metal salts and amides. on the other hand,
As the fluidizing agent used as an external additive, for example, inorganic fine particles having a particle size of several tens of nm, specifically, colloidal silica, alumina, titanium oxide, zinc oxide, magnesium fluoride, silicon carbide, boron carbide, titanium carbide , Zirconium carbide, boron nitride, titanium nitride, zirconium nitride, magnetite, molybdenum disulfide, aluminum stearate, magnesium stearate, zinc stearate and the like. The fluidizing agent may be subjected to a hydrophobic treatment with a silane-based or titanium-based coupling agent, a higher fatty acid, silicone oil, a surfactant, or the like.

Examples of the cleaning aid used as an external additive include fine particles such as polystyrene, polymethyl methacrylate, polyacrylate, polybenzoguanamine, silicone resin, polytetrafluoroethylene, polyethylene, and polypropylene. The method for preparing the toner of the present invention is not particularly limited, and conventionally known methods such as a mechanical pulverization method, a spray drying method, a chemical polymerization method, and a chemical granulation method can be applied. Of these, the mechanical pulverization method involves dry-blending the above-mentioned toner components, melt-kneading them, then coarsely pulverizing them, and finally pulverizing them with a jet pulverizer or the like. Therefore, this is a method in which fine particles having a volume average particle size of about 5 to 20 μm are obtained by performing classification. The electrophotographic toner thus prepared is mixed with carrier particles and used as a developer for two-component development, or used alone as a developer for one-component development. Here, as the carrier, for example, a magnetic powder carrier, a magnetic powder resin-coated carrier, a binder carrier, a glass bead, or the like is applied. The particle size of these carriers is usually about 20 to 500 μm. Examples of magnetic powder carriers include metals such as iron, nickel, ferrite, magnetite, and cobalt;
Alloys with metals such as antimony, aluminum, lead, tin, bismuth, beryllium, manganese, selenium, tungsten, zirconium, vanadium or mixtures thereof, metal oxides such as iron oxide, titanium oxide, magnesium oxide,
Nitrides such as chromium nitride and vanadium nitride, silicon carbide,
A mixture with a carbide such as tungsten carbide is applied.

As the magnetic powder resin-coated carrier, a carrier coated with the following resin using the above magnetic component particles as a core material is used. As the coating resin, for example, polyethylene,
Silicone resin, fluorine resin, styrene resin, acrylic resin, styrene-acrylic resin, polyvinyl acetate, cellulose derivative, maleic acid resin, epoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyodor Vinylidene fluoride, polycarbonate, polyester, polypropylene, phenolic resin, polyvinyl alcohol, fumaric acid ester resin, polyacrylonitrile, polyvinyl ether, chloroprene rubber, acetal resin, ketone resin, xylene resin, butadiene rubber, styrene-butadiene copolymer, polyurethane, etc. Is the use. The magnetic powder resin-coated carrier includes conductive fine particles (carbon black, conductive metal oxide, metal powder), inorganic fillers (silica, silicon nitride, boron nitride, alumina, zirconia, silicon carbide, boron carbide,
Titanium oxide, clay, talc, glass fiber), the charge control agent exemplified above, and the like may be contained as necessary. The thickness of the resin coating on the carrier core material is preferably about 0.1 to 5 μm. The electrophotographic toner of the present invention is used after being transferred and fixed to a support (paper, OHP film such as polyester). As the fixing method, for example, pressure fixing, heat fixing (SURF fixing, fixing using a hot plate, oven fixing, infrared lamp fixing, etc.), contact heating pressure fixing, flash fixing, solvent fixing, etc. can be applied. Pressure fixing is preferred.

The toner of the present invention can be applied to any type of magnetic one-component development, magnetic two-component development, non-magnetic one-component development, non-magnetic two-component development and liquid development. It is advantageously used for development, magnetic two-component development and non-magnetic one-component development. The toner of the present invention can be applied to various developing methods. For example, a magnetic brush developing method, a cascade developing method, a method using a conductive magnetic toner described in US Pat. No. 3,909,258, a method using a high-resistance magnetic toner described in JP-A-53-31136, JP 54
-42121, 55-18656, 5
4-43027, fur brush development method, powder cloud method, impression development method, microtoning method, contact development method, touchdown development method, magnetodynamic development method, jumping development method, FEED (Floating Electrode Effect
Development) development method, FMT (Fine Micro Toning Syst
em) Development method, NSP (Non Magnetic Single Component
Development Process) It can be applied to a development method and the like.

The toner of the present invention can be applied to any machine of corona charging (corotron type, scorotron type, etc.) and contact charging (charging roll type, charging brush type, etc.). Further, a method without a cleaning step, a blade method, a fur brush method, a magnetic brush method, a roller cleaning method and the like can be applied, but a method without a blade method and a cleaning step is preferable. Next, the toner of the present invention comprises an organic electrophotographic photoreceptor (laminated type, single layer type) and an inorganic photoreceptor (amorphous silicon, amorphous selenium,
The present invention can be applied to any of selenium-based photoconductors and germanium-based photoconductors, and is particularly preferably applied to organic electrophotographic photoconductors and inorganic photoconductors using amorphous silicon. Further, the toner of the present invention is applicable to both (1) the reversal development process and the normal development process.
(2) Applicable to both positively and negatively charged toners; (3) Applicable to both monochrome and color printing presses; (4) Applicable to both analog and digital printing presses (5) Applicable to copiers, printers (laser beam printers, liquid crystal shutter printers, etc.), facsimile machines, and multifunction peripherals thereof.

[0023]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The softening point (Tm), bromine value and Gardner color number of each resin were measured according to the following methods. (1) Softening point (Tm) Measured by the ring and ball method according to JIS K-2207. (2) Bromine value It was measured according to JIS K-2605. (3) Gardner color number Measured in accordance with JIS K-6901 (1995), 4.2.2 Gardner color number method.

Example 1 (1) Production of Petroleum Resin 154 g of xylene was placed in a 1 liter autoclave equipped with a stirrer and purged with nitrogen, and 269 g of dicyclopentadiene and styrene 2 were heated to 230 ° C. and stirred.
The mixture with 69 g was added over 2 hours. Thereafter, the temperature of the reaction solution was raised to 260 ° C. over 105 minutes, followed by a reaction for 4 hours. After the completion of the reaction, the reaction product liquid is taken out, and treated with a rotary evaporator at a temperature of 200 ° C. and a pressure of 10 mmHg for 3 hours to remove unreacted monomers and xylene, thereby obtaining 510 g of a copolymer of dicyclopentadiene and styrene. Obtained. The softening point of this copolymer is 115
° C, the content of aromatic ring (based on styrene) was 43% by weight, and the bromine value was 54 g / 100 g. Next, 75 g of cyclohexane and 75 g of the copolymer obtained above were placed in a 300 ml autoclave equipped with a stirrer and purged with nitrogen.
A 4.0% by weight silica-alumina catalyst supported on palladium was charged and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and a temperature of 150 ° C. for 2 hours. The softening point of this hydrogenated resin is 120 ° C.
The aromatic ring content (based on styrene) was 43% by weight, the bromine number was 14 g / 100 g, and the Gardner color number was 3.

(2) Preparation of toner 86 parts by weight of the hydrogenated resin obtained in (1) above,
Butadiene resin ("Priolite S" manufactured by Goodyear)
-5B "), 7 parts by weight of wax (" Paraflint C105 ", manufactured by Sasol), 7 parts by weight of carbon black (" MA100 ", manufactured by Mitsubishi Chemical Corporation), and a charge control agent (" SP100 "manufactured by Hodogaya Chemical Industry Co., Ltd.) Ronblack TRH ”) were sufficiently mixed with a Hensiel mixer, and then melt-kneaded with a twin-screw extruder. After cooling, the kneaded product was coarsely pulverized by a hammer mill, finely pulverized by a jet mill, and then classified by a classifier to prepare a toner having a volume average particle diameter of 8 μm.

Example 2 (1) Production of Petroleum Resin 260 g of xylene was placed in a 1-liter autoclave equipped with a stirrer and purged with nitrogen, and 216 g of dicyclopentadiene and styrene 2 were heated to 260 ° C. and stirred.
After adding the mixture with 16 g over 2 hours, 4
Allowed to react for hours. After the reaction, take out the reaction product liquid,
Using a rotary evaporator, the mixture was treated at a temperature of 200 ° C. and a pressure of 10 mmHg for 3 hours to remove unreacted monomers and xylene to obtain 510 g of a copolymer of dicyclopentadiene and styrene. The softening point of this copolymer is 10
At 0 ° C., the aromatic ring content (based on styrene) was 44% by weight, and the bromine value was 56 g / 100 g. Next, 75 g of cyclohexane, 75 g of the copolymer obtained above, and 2.0 g of a nickel catalyst (“N-113” manufactured by Nikki Chemical Co., Ltd.) were charged into a 300 ml autoclave equipped with a stirrer replaced with nitrogen, and hydrogen pressure was 4 MPa. A hydrogenation reaction was performed at a temperature of 230 ° C. for 3 hours. The hydrogenated resin has a softening point of 120 ° C., an aromatic ring content (based on styrene) of 20% by weight, and a bromine number of 3%.
g / 100 g, and the Gardner color number was 1 or less. (2) Preparation of Toner Example 1 was prepared using the hydrogenated resin obtained in (1) above.
A toner was prepared in the same manner as in (2).

Example 3 (1) Production of Petroleum Resin In a 300 ml autoclave equipped with a stirrer and purged with nitrogen, 75 g of cyclohexane, 75 g of the copolymer before hydrogenation obtained in Example 1- (1), 0.5% by weight 4.0 g of a silica-alumina catalyst supported on palladium and charged with hydrogen pressure 4
A hydrogenation reaction was performed at a pressure of 200 ° C. for 45 minutes. The hydrogenated resin has a softening point of 122 ° C., an aromatic ring content (based on styrene) of 32% by weight, and a bromine number of 25 g / 10.
0 g and the Gardner color number was 5. (2) Preparation of Toner Example 1 was prepared using the hydrogenated resin obtained in (1) above.
A toner was prepared in the same manner as in (2).

Example 4 (1) Production of Petroleum Resin 154 g of xylene was placed in a 1 liter autoclave equipped with a stirrer and purged with nitrogen, and 289 g of dicyclopentadiene and styrene 2 were heated to 260 ° C. and stirred.
After addition of the mixture with 69 g over 2 hours, 2
The reaction was carried out at 60 ° C. for 4 hours and 30 minutes. After the completion of the reaction, the reaction product liquid was taken out and treated at a temperature of 200 ° C. and a pressure of 10 mmHg for 3 hours using a rotary evaporator.
The unreacted monomer and xylene were removed to obtain 510 g of a copolymer of dicyclopentadiene and styrene. This copolymer had a softening point of 120 ° C., an aromatic ring content (based on styrene) of 46% by weight, a bromine number of 57 g / 100 g, and a Gardner color number of 7. (2) Preparation of Toner Example 1 was prepared using the copolymer obtained in (1) above.
A toner was prepared in the same manner as in (2).

Example 5 (1) Production of Petroleum Resin In a 2 liter reactor equipped with a stirrer, a cooler and a catalyst injection device, 32.3 parts by weight of an α-pinene concentrate obtained by cracking a petroleum raw material, 27.7 parts by weight of piperylene concentrate,
10 parts by weight of styrene and 30 parts by weight of a solvent containing paraffin as a main component were charged. 1 to the total weight of this mixture
After injecting into the reactor by weight of powdered aluminum chloride as a catalyst, it was kept at 50-60 ° C. for 90 minutes. Thereafter, the reaction was stopped by adding an ammonia solution, and then steam stripping was performed at 250 ° C. in a nitrogen atmosphere to obtain a copolymer. The softening point of this copolymer was 109 ° C., and the Gardner color number was 3. (2) Preparation of Toner Example 1 was prepared using the copolymer obtained in (1) above.
A toner was prepared in the same manner as in (2).

Comparative Example 1 (1) Production of Petroleum Resin In a 1-liter reactor equipped with a stirrer, a cooler and a thermometer, a C5 cut obtained by naphtha cracking was used as a starting material.
0, -dihydrodicyclopentadiene-containing fraction 340
g, indene 29 g, and disilodipentadiene 132 g. This was mixed with a boron trifluoride phenol complex catalyst (boron trifluoride content 3
(0% by weight) A mixture of 6.6 g and 46 g of toluene was dropped in about 20 minutes using a syringe. Cooling and warming were maintained at 60 ° C. After polymerization for 2 hours, an aqueous sodium hydroxide solution was added to decompose the catalyst, followed by washing with water and concentration to obtain 83 g of a copolymer. The softening point of this copolymer is 7
9 ° C, bromine number 71g / 100g, Gardner color number 1
It was one. (2) Preparation of Toner Example 1 was prepared using the copolymer obtained in (1) above.
A toner was prepared in the same manner as in (2).

Comparative Example 2 Using an aromatic petroleum resin having a Gardner color number of 13 ("Petrosin # 100" manufactured by Mitsui Petrochemical Co., Ltd.),
A toner was prepared in the same manner as in (2). The toners obtained in the above Examples 1 to 5 and Comparative Examples 1 and 2 were applied to an electrophotographic dry copying machine (PPC) of a heat roller fixing method, where actual copying was performed and the color reproducibility of an output image was obtained. Was evaluated. The evaluation of color reproducibility was as follows: o, those which showed a clear color corresponding to the color of the toner image visually, Δ, which was dark, and X, which was extremely unclear.
And Table 1 shows the evaluation results of the color reproducibility.

[0032]

[Table 1]

[0033]

The toner binder resin of the present invention is a toner binder resin used for electrophotographic copying machines, printers, facsimile machines, etc., and provides an image having excellent image density and color reproducibility at intermediate gradations. Can be provided.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshihiro Mine 1-1, Shingucho, Tokuyama-shi, Yamaguchi

Claims (4)

[Claims] 1. A toner binder resin for electrophotography, comprising a petroleum resin having a Gardner color number of 10 or less. 2. The toner binder resin according to claim 1, wherein the petroleum resin has a Gardner color number of 5 or less. 3. The toner binder resin according to claim 2, wherein the petroleum resin has a Gardner color number of 2 or less. 4. An electrophotographic toner comprising the binder resin according to claim 1, 2 or 3 as a toner resin.