JPH1152614A - Toner binder resin, and toner using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide binder resin for toner for development of an electrostatic image which is excellent in low temperature fixing capability, blocking resistance, tacking resistance, and toner crushing capability, and toner using same. SOLUTION: Binder resin for toner for development of an electrostatic image comprises at least one sort selected among resin obtained by polymerization of at least one sort of monomer of cyclopentadiene, dicyclopentadiene, and dihydrodicyclopentadiene, copolymer resin obtained by polymerization of above monomer with other polymerization monomer, and hydrogen additive of such resin, and toner for development of an electrostatic image comprises the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner binder resin and an electrostatic image developing toner using the same, and more particularly, to an electrophotographic method, an electrostatic recording method, an electrostatic printing method and the like. Low-temperature fixability, anti-blocking properties used to develop electrostatic latent images formed in
The present invention relates to a binder resin which provides a toner having good tack resistance and toner crushability, and a toner having the above-mentioned performance using the binder resin.

[0002]

2. Description of the Related Art In recent years, low-temperature fixing type toners have been actively developed in order to achieve colorization and energy saving of electrophotographic copying machines and printers. To achieve this low-temperature fixing, the softening temperature (Tm) of the toner resin
It is effective to lower the Tm, but generally, when the Tm is lowered, the glass transition temperature (Tg) of the toner is also lowered. This causes the fixing temperature to be lowered as desired. In order to satisfy the conflicting requirements of low-temperature fixing property and blocking resistance, for example, (1) a method of using a polyester resin having a high affinity for paper and having a low fixing temperature in spite of a high Tm or Tg (particularly, 56-19 Kaisho
No. 52), (2) Toner using a petroleum resin having excellent melting properties and excellent low-temperature fixability (JP-A-4-257868).
JP-A-8-278658, and (3) a toner using a hydrogenated petroleum resin.

However, in the method (1) using a polyester resin, although low-temperature fixability and blocking resistance have been improved to some extent, a toner which can sufficiently satisfy both at the same time has not been obtained. Moreover, the polyester resin has a high cohesive energy density, and thus has a drawback such as difficulty in pulverization during toner production. On the other hand, in the toner using the petroleum resin (2) and the toner using the hydrogenated petroleum resin (3), the low-temperature fixability is improved to some extent, and there is a problem in the production of the toner which has a problem with the polyester resin. Although the pulverizability is extremely good, the low-temperature fixability is still not sufficiently satisfactory, and the storage stability of the toner has a little tackiness (stickiness) of a conventionally known petroleum resin. Therefore, even when the Tg of the toner is high, the toner may be agglomerated, which is not sufficient.

In the specification and examples of Japanese Patent Application Laid-Open No. 8-278658, the partially hydrogenated C6-C8 aromatic hydrocarbon-dicyclopentadiene copolymer has anti-blocking properties and low-temperature fixing properties. There is a statement that it is excellent. However, the hydrogenation rate, that is, the value of [(Iodine value of the resin-Iodine value of the completely hydrogenated resin) / (Iodine value of the unhydrogenated resin-Iodine value of the completely hydrogenated resin)] × 100 (%) Is controlled to 50% or more to exhibit low-temperature fixability and blocking resistance, and there are various restrictions in applying a petroleum resin to toner. Further, the toner binder resin disclosed in the above publication is substantially composed of another resin (styrene-acrylic resin, polyester resin, etc.) and the petroleum resin, and the content of the petroleum resin is 70 in each of the specific examples. The composition was less than wt%. In such a configuration, the low-temperature fixability and the good pulverizability at the time of toner production, which are inherent properties of petroleum resin, have not been sufficiently exhibited.

[0005]

SUMMARY OF THE INVENTION The present invention provides a toner for developing an electrostatic image capable of sufficiently satisfying the low-temperature fixing property, the blocking resistance, the tack resistance and the toner pulverizability at the same time. An object of the present invention is to provide a toner binder resin and a toner for developing an electrostatic image having the above-mentioned excellent performance using the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the tackiness of petroleum resin is because the resin raw material itself is a mixture of monomers having a wide range of properties. Focusing on the fact that petroleum resin becomes a resin mixture with a complicated structure and sometimes contains low-polymerized products, it has a specific structure and distillation from the fraction obtained by pyrolysis of petroleum naphtha. Resins consisting of monomers having properties, in particular, cyclopentadiene, dicyclopentadiene or dihydrodicyclopentadiene as monomers, and resins obtained by polymerizing them, copolymer resins of these with other polymerizable monomers, or It has been found that a hydrogenated product of the above resin is suitable for the purpose as a toner binder resin. The present invention has been completed based on such findings. That is, the present invention relates to (1) (A) a resin obtained by polymerizing at least one monomer of cyclopentadiene, dicyclopentadiene and dihydrodicyclopentadiene; and (B) a carbon-carbon unsaturated bond of the resin. A toner binder resin for developing an electrostatic image composed of at least one selected from resins obtained by hydrogenating part or all of
(2) (A ′) a copolymer resin obtained by polymerizing at least one monomer of cyclopentadiene, dicyclopentadiene and dihydrodicyclopentadiene with another polymerizable monomer, wherein the other polymerizable monomer is Is 90% by weight
The following resin, and (B ′) the carbon-
As the toner binder resin for developing an electrostatic image formed of at least one selected from resins obtained by hydrogenating part or all of carbon unsaturated bonds and / or aromatic rings, and (3) the toner resin described above ( An object of the present invention is to provide a toner for developing an electrostatic image, comprising the binder resin of (1) or (2).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The toner binder resin of the present invention comprises the following (A), (B), (A ') and (B').
Of at least one resin selected from the above resins. First, the resin (A) is a copolymer comprising at least two selected from cyclopentadiene polymer, dicyclopentadiene polymer, dihydrodicyclopentadiene polymer or cyclopentadiene, dicyclopentadiene and dihydrodicyclopentadiene. Or a mixture thereof. These resins are obtained by polymerizing monomers by, for example, cationic polymerization, radical polymerization, thermal polymerization, anionic polymerization, ionic coordination polymerization, suspension polymerization, emulsion polymerization, or polymerization using a transition metal complex. , A low-polymer or a solvent can be removed by means such as distillation.

The resin (B) is obtained by hydrogenating a part or all of the carbon-carbon unsaturated bonds of the resin (A) obtained as described above. There is no particular limitation on the hydrogenation method, and a conventionally known method can be used. Next, the resin (A ') is a copolymer resin obtained by polymerizing at least one monomer of cyclopentadiene, dihydrodicyclopentadiene and dihydrodicyclopentadiene with another polymerizable monomer, A resin having a polymerizable monomer content of 90% by weight or less, preferably 80 to 10% by weight. This copolymer resin is obtained by polymerizing a monomer by, for example, cationic polymerization, radical polymerization, thermal polymerization or the like, as in the case of the resin (A), and then unreacted monomer, low-polymerized product, solvent, or the like is distilled out or the like. By removing it, it can be manufactured.

The other polymerizable monomer is preferably an aromatic ring-containing vinyl compound having 8 to 13 carbon atoms. Examples of the aromatic ring-containing vinyl compound include α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, alkyl-substituted indene, allylbenzene, allyltoluene, tert-butylstyrene, and tert-butylallylbenzene. At least one selected is given. In addition, styrene can also be used as a copolymer monomer. In addition, other known monomers such as olefins having 2 to 20 carbon atoms such as ethylene, propylene, cyclopentene, cyclohexene, 1-octene, and pinene, and 4 to 20 carbon atoms such as butadiene, isoprene, pentadiene, limonene, and myrcene. Polyenes, (meth) acrylates such as methyl, ethyl, butyl, octyl, phenyl, stearyl esters of (meth) acrylic acid, vinyl chloride; vinylidene chloride; 1,2-dichloroethylene; trichloroethylene; tetrachloroethylene; vinyl fluoride Vinylidene fluoride; 1,2-difluoroethylene;
Trifluoroethylene; tetrafluoroethylene; halogenated vinyls such as vinyl bromide, vinylsilanes such as trialkylvinylsilane and trialkoxyvinylsilane, α, β-unsaturated ketones such as methyl vinyl ketone and phenyl vinyl ketone, and the like. Acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, maleic acid, maleic ester, maleic anhydride, cyclopropane and its derivatives, cyclobutane and its derivatives, oxetane and its derivatives, tetrahydrofuran and its derivatives, acetylene and its derivatives, α, Examples include β-unsaturated aldehydes, α, β-unsaturated esters, and dithiols having 2 to 10 carbon atoms.

Further, the resin (B ') is obtained by hydrogenating a part or all of carbon-carbon unsaturated bonds and / or aromatic rings of the copolymer resin (A') obtained as described above. Things. There is no particular limitation on the hydrogenation method, and a conventionally known method can be used. As the toner binder resin of the present invention, among these resins,
Dicyclopentadiene-styrene copolymer resin having a styrene unit content of 90% by weight or less, dicyclopentadiene-
Indene copolymer resin, dicyclopentadiene-indene-styrene copolymer resin (indenes: indene,
Styrenes such as methylindene; styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, dicyclopentadienes: dicyclopentadiene, dihydrodicyclopentadiene, etc.), dicyclopentadiene resins, and resins of these resins A resin obtained by hydrogenating part or all of a carbon-carbon unsaturated bond and / or an aromatic ring is preferable, and the above-mentioned dicyclopentadiene-styrene copolymer resin and a hydrogenated product thereof are particularly preferable.

The toner binder resin of the present invention preferably has a number average molecular weight in the range of 400 to 3000. Further, those having a softening point in the range of 80 to 140 ° C are preferred, and those having a softening point in the range of 100 to 130 ° C are particularly preferred. Further, as the toner binder resin, when the bromine value of the binder resin is a and the bromine value of the binder resin before hydrogenation is c, the one having an a / c value of 0.45 or less is particularly preferable in blocking resistance. Excellent and suitable. This numerical value is a numerical value representing the hydrogenation rate described in JP-A-8-278658 [(Iodine value of the resin-Iodine value of the completely hydrogenated resin) / (Iodine value of the unhydrogenated resin-Fully) Iodine value of hydrogenated resin)] × 100 (%);
They are substantially synonymous (because bromine value = iodine value × 0.630 and the bromine value and iodine value of a completely hydrogenated resin can be approximated to 0). Such a toner binder resin of the present invention is particularly suitable as a binder resin for a toner for fixing a contact heating pressure by a heat roll. Next, the toner for developing an electrostatic image 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 further improved, and Tm can be greatly reduced without substantially lowering 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 preferable. In addition, styrene oligomer, amorphous poly-α-
Olefins are also preferably used. Among them, Fischer-Tropsch wax and styrene oligomer are particularly preferable.

These waxes may be used alone or in a 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. The toner of the present invention preferably has a minimum fixing temperature of 140 ° C. or lower, particularly preferably 130 ° C. or lower.

[0015] In addition, within a range that does not impair the effects of the present invention,
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 (C ₂ -C ₁₂ ) such as propylene glycol, 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 component: aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, trivalent or higher polycarboxylic acid), polystyrene, chloropolystyrene , Poly-α-methylstyrene, poly-4-methoxystyrene, poly-4-hydroxystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyl chloride copolymer, styrene-male Acid copolymer, styrene-vinyl acetate copolymer, styrene-acrylic acid ester copolymer (methyl, ethyl, butyl, octyl, phenis ester), styrene-methacrylic acid ester copolymer (methyl, ethyl, butyl, Octyl, phenyl ester), styrene-α-chloromethyl acrylate copolymer, styrene-acrylonitrile-acrylate copolymer, α-methylstyrene-acrylate copolymer (methyl, ethyl, butyl, octyl, phenyl) Ester), α-methylstyrene-methacrylic acid ester copolymer (methyl, ethyl, butyl, octyl, phenylester), α-methylstyrene-α-chloromethyl acrylate copolymer, α-methylstyrene-acrylonitrile-acryl Acid ester copolymer, vinyl chloride Fat, rosin-modified maleic acid resins, phenol resins, epoxy resins, polyethylene resins, polypropylene resins, ionomer resins, polyurethane resins, silicone resins,
Ketone resin, ethylene-ethyl acrylate copolymer,
Xylene resin, polyvinyl butyral resin and the like can be mentioned. 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. The toner of the present invention or the toner resin used therein may further contain other additives such as an antioxidant, an antiozonant, an ultraviolet absorber, a light stabilizer, and the like, 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 developing an electrostatic image of the present invention is usually
25 to 95% by weight of toner binder (toner resin), 0 to 10% by weight of colorant, 0 to 70% by weight of magnetic powder, 0 to 10% by weight of charge control agent and 0 to 10% by weight of lubricant, and further an external additive As a fluidizer, 0 to 1.5% by weight of a fluidizing agent and 0 to 1.5% of a cleaning aid are added. 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 Industry Co., Ltd.) and P-51 (Orient Chemical Corporation). 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, metal dicarboxylate, 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, decyl-trimethylammonium 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 polytetrafluoroethylene, low molecular weight polyolefin, fatty acid and its metal salts and amides. On the other hand, as a 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, Examples include titanium carbide, zirconium carbide, boron nitride, titanium nitride, zirconium nitride, magnetite, molybdenum disulfide, aluminum stearate, magnesium stearate, and zinc stearate. 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 wet 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 toner for developing an electrostatic charge image thus prepared is mixed with carrier particles and used as a developer for two-component development, or the toner alone is used as a developer for one-component development. used. 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 20-500 μm
It is about. Examples of magnetic powder carriers include metals such as iron, nickel, ferrite, magnetite, and cobalt;
These metals and zinc, antimony, aluminum, lead,
Alloys or mixtures with metals such as tin, bismuth, beryllium, manganese, selenium, tungsten, zirconium, and vanadium, metal oxides such as iron oxide, titanium oxide, and magnesium oxide; nitrides such as chromium nitride and vanadium nitride; and carbonized A mixture with a carbide such as silicon or tungsten carbide is applied.

As the magnetic powder resin-coated carrier, a carrier obtained by coating the above magnetic component particles as a core material with the following resin 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 electrostatic image developing toner of the present invention is used after being transferred and fixed onto 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 is applicable 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.

[0025]

Next, the present invention will be described in more detail by way of examples.
However, the present invention is in no way limited by these examples.
Not something. The softening point (Tm) of each resin, bromine
Value, average molecular weight, aromatic ring content, aromatic ring hydrogenation rate
Measured according to the method. (1) Softening point (Tm) Measured by the ring and ball method according to JIS K-2207.
Was. (2) Bromine value It was measured according to JIS K-2605. (3) Average molecular weight Gel permeation chromatography (GPC) method
The number average molecular weight and weight average in terms of polystyrene
The molecular weight was measured. (4) Aromatic ring content It was analyzed by infrared absorption spectroscopy. Solvent is carbon disulfide
Use, wave number 700cm ^-1Was determined from the absorbance at (5) Aromatic ring hydrogenation rate Aromatic ring hydrogenation rate (%) = [1- (aromatic ring content of hydrogenated resin)
/ Aromatic ring content of unhydrogenated resin)] × 100.

Synthesis Example 1 A 2-liter autoclave was charged with dicyclopentadiene 6
40 g and 160 g of xylene were charged under nitrogen atmosphere.
From the polymer solution obtained by reacting at 60 ° C. for 45 minutes,
By removing unreacted substances, low-polymerized substances and xylene by distillation, resin A (softening point: 116 ° C., bromine number: 11) was obtained.
5 g / 100 g). In a 500 ml autoclave equipped with a stirrer, 100 g of resin A, 100 g of methylcyclohexane, and 3 g of a nickel catalyst (“N-113” manufactured by JGC Chemicals, Inc.) were charged, and a hydrogenation reaction (50 kg /
cm ² · G, 250 ° C., 2 hours), the reaction product was cooled and taken out, filtered to remove the catalyst, and then the solvent was removed by distillation to obtain a hydrogenated resin A (softening point: 112 ° C., bromine). Price:
5 g / 100 g, bromine value of hydrogenated resin / bromine value of unhydrogenated resin] (hereinafter a / c): 0.043].

Synthesis Example 2 In a 1-liter autoclave, dicyclopentadiene 2 was added.
20 g, 144 g of styrene, 36 g of indene and 40 g of toluene were charged and reacted under a nitrogen atmosphere at 275 ° C. for 3 hours. From the polymer solution obtained, unreacted substances and low-polymerized substances were removed by distillation to obtain resin B. (Softening point: 97
° C, bromine number: 135 g / 100 g). In a 500 ml autoclave equipped with a stirrer, add resin B80
g, cyclohexane 80 g, nickel catalyst (2 g of “N-113” manufactured by JGC Chemicals Co., Ltd.) and hydrogenation reaction (15
0 kg / cm ² · G, 300 ° C., 2 hours), the reaction product was cooled and taken out, filtered to remove the catalyst, and then the solvent was removed by distillation to obtain a hydrogenated resin B (softening point: 104 ° C.). ,
Bromine value: 5 g / 100 g, a / c: 0.037).

Synthesis Example 3 In a 1-liter autoclave, dicyclopentadiene 3 was added.
68 g, styrene 21 g, indene 11 g, toluene 4
0 g, and reacted under a nitrogen atmosphere at 275 ° C. for 3 hours to remove unreacted substances and low-polymerized substances by distillation, thereby obtaining resin C (softening point: 97 ° C.).
° C, bromine number: 148 g / 100 g, number average molecular weight (M
n): 400) was obtained. In a 500 ml autoclave equipped with a stirrer, 80 g of resin C, 80 g of cyclohexane, and a nickel catalyst ("N-11" manufactured by JGC Chemicals, Inc.)
3 ", 2 g, and hydrogenation reaction (150 kg / cm ² ·
G, 300 ° C., 2 hours), the reaction product was cooled and taken out, filtered to remove the catalyst, and then the solvent was removed by distillation to obtain a hydrogenated resin C (softening point: 105 ° C., bromine number: 3). .2g1
00g, a / c: 0.022).

Synthesis Example 4 A C5 fraction obtained by naphtha decomposition was heated at 150 ° C. for 3 hours to convert cyclopentadiene contained in the distillate into dicyclopentadiene, and then a light distillate was removed by distillation.
A crude dicyclopentadiene containing 75% by weight or more of dicyclopentadiene was obtained. 800 g of the obtained crude dicyclopentadiene and 30 g of a palladium-based tablet-type hydrogenation catalyst (C31-1A, manufactured by Toyo CCI Co., Ltd.) were charged into a 2-liter stainless steel autoclave, and the reaction temperature was 50 ° C. and the hydrogen pressure was 10 kg / cm. ^The mixture was stirred at ² · G for 12 hours to perform a hydrogenation reaction. The catalyst is removed by filtration, and a fraction D (pentanes: 10% by weight, mainly containing 9,10-dihydrodicyclopentadiene) is removed by distillation.
9,10-dihydrodicyclopentadiene: 81% by weight, dicyclopentadiene: 0.1% by weight or less, tetrahydrodicyclopentadiene: 2% by weight, unknown component: 7% by weight, the above composition is determined by gas chromatography analysis). Obtained.

Synthesis Example 5 Naphtha-cracked oil was distilled in an Oldershaw type 40-stage distillation column, and a fraction E (styrene + α-methylstyrene + vinyltoluene having a boiling point of 50 to 65 ° C./10 mmHg and containing indene and methylindene as main components: 10% by weight, dicyclopentadiene: 5% by weight, indene: 30% by weight, methylindene: 16% by weight, and the above composition was determined by gas chromatography analysis).

Synthesis Example 6 In a 1 liter four-necked flask equipped with a stirrer, a Liebig condenser, and a thermometer, 310 g of the fraction D, 58 g of indene,
33 g of dicyclopentadiene were added. Under a nitrogen atmosphere, 6.6 g of a boron trifluoride phenol complex catalyst (boron trifluoride content: 30% by weight) and toluene
0 g of the mixture was dropped using a syringe over about 20 minutes. While maintaining the reactor internal temperature at 60 ° C., stirring was further performed for 3 hours. An aqueous solution of sodium hydroxide was added to the obtained reaction mixture to decompose the catalyst, followed by washing with water. By distilling the organic layer to remove unreacted substances and low-polymerized substances, resin F (softening point: 104 ° C., bromine number: 60 g / 100 g,
(Number average molecular weight: 430) 130 g was obtained.

[0032] Synthesis Example 7 stirrer, Liebig condenser, a thermometer, a four-necked flask of one liter with a dropping funnel, powdered AlCl ₃
2.6 g and 40 g of xylene were stirred in a slurry state under a nitrogen atmosphere, and heated to 50 ° C. Using a dropping funnel, a mixture of 170 g of fraction D, 80 g of fraction E, and 33 g of dicyclopentadiene was added dropwise over about 30 minutes. Stirring was further performed for 4 hours while maintaining the internal temperature of the reactor at 50 ° C. After methanol was added to the obtained reaction mixture to decompose the catalyst, the mixture was washed with water. By distilling the organic layer to remove unreacted substances, low-polymerized substances, and methanol, Resin G (softening point: 105 ° C., bromine number: 66 g / 1)
00g, number average molecular weight: 450) 80 g was obtained.

Synthesis Example 8 A 1-liter four-necked flask equipped with a stirrer, a Liebig condenser and a thermometer was charged with 64 g of fraction D and 284 g of fraction E. Under a nitrogen atmosphere, a mixed solution of 4.4 g of a boron trifluoride phenol complex catalyst (boron trifluoride content: 30% by weight) and 20 g of xylene was added dropwise with a syringe over about 20 minutes while stirring. While maintaining the reactor internal temperature at 60 ° C., stirring was further performed for 2 hours. After adding an aqueous sodium hydroxide solution to the obtained reaction mixture to decompose the catalyst,
Washing was performed. By distilling the organic layer to remove unreacted substances, low-polymerized substances and xylene, the resin H (softening point: 1) was obtained.
22 ° C, bromine number: 44 g / 100 g, number average molecular weight: 4
80) 160 g were obtained.

Synthesis Example 9 68 g of 1,2-dihydrodicyclopentadiene, 58 g of indene and 3 g of dicyclopentadiene were placed in a 1-liter four-necked flask equipped with a stirrer, a Liebig condenser, and a thermometer.
3 g and 94 g of toluene were added. In a nitrogen atmosphere,
With stirring, a complex catalyst of boron trifluoride phenol (boron trifluoride content: 30% by weight) (6.6 g) was added dropwise using a syringe over about 20 minutes. Stirring was further performed for 3 hours while maintaining the internal reaction temperature at 60 ° C. An aqueous solution of sodium hydroxide was added to the obtained reaction mixture to decompose the catalyst, followed by washing with water. By distilling the organic layer to remove unreacted substances and low-polymerized substances, the resin I (softening point: 100 ° C.,
Bromine value: 65 g / 100 g, number average molecular weight: 440) 1
10 g were obtained.

Synthesis Example 10 Xylene 14 was used as a solvent in a 1-liter autoclave.
0 g, heated to 260 ° C. under a nitrogen atmosphere, and 68.8 g of dicyclopentadiene and styrene 3 were stirred.
90 g of the mixture were added over 2 hours. The reaction was continued at the same temperature for another 400 minutes. From the obtained polymer solution, unreacted substances and low-polymerized substances were removed by distillation to obtain resin J (styrene unit / dicyclopentadiene (DCPD) unit weight ratio = 85/15, number average molecular weight: 760, Softening point: 102 ° C, bromine number: 35 g /
100 g).

Synthesis Example 11 Xylene 140 was used as a solvent in a 1 liter autoclave.
g, heated to 260 ° C. in a nitrogen atmosphere, and stirred while stirring 22.9 g of dicyclopentadiene and 43% of styrene.
5.8 g of the mixture was added over 2 hours. The reaction was continued at the same temperature for another 800 minutes. From the obtained polymer solution, unreacted substances and low-polymerized substances were removed by distillation to obtain resin K (weight ratio of styrene unit / DCPD unit = 95/5, number average molecular weight: 770, softening point: 1).
04 ° C., bromine number: 18 g / 100 g). Also, 1
A liter autoclave was charged with 250 g of resin K, 250 g of cyclohexane and 3.0 g of a Pd-alumina catalyst containing 0.5% by weight of Pd, and a hydrogen pressure of 30 kg / cm ^2.
G, a hydrogenation reaction was carried out at a temperature of 150 ° C. for 30 minutes, the reaction product was cooled and taken out, and after filtering to remove the catalyst, the solvent was removed by distillation to obtain a hydrogenated resin K-2 (softening point: 1
06 ° C., bromine number: 11 g / 100 g, a / c: 0.61)
I got

Synthesis Example 12 Dicyclopentadiene 28 was added to a 1-liter autoclave.
0 g and isoprene (120 g) were charged and reacted under a nitrogen atmosphere at a pressure of 10 kg / cm ² · G at 260 ° C. for 4 hours to remove unreacted substances and low-polymerized substances by distillation. Resin L (softening point: 108 ° C,
Bromine value: 84 g / 100 g). 5 with stirrer
In a 00 ml autoclave, 100 g of resin L, 100 g of cyclohexane, nickel catalyst (Nikki Chemical Co., Ltd.)
3 g of "N-113M" manufactured by
g / cm ² · G, 200 ° C., 3 hours), the reaction product is cooled and taken out, filtered to remove the catalyst, and then the solvent is removed by distillation to obtain a hydrogenated resin L (softening point: 113 ° C.). , 1.5 / 100 g, a / c: 0.018).

Synthesis Example 13 Dicyclopentadiene 28 was added to a 1-liter autoclave.
0 g and 120 g of 1,3-pentadiene were charged and reacted under a nitrogen atmosphere at a pressure of 10 kg / cm ² · G at 260 ° C. for 4 hours to remove unreacted substances and low-polymerized substances by distillation. By doing so, the resin M (softening point:
110 ° C., bromine value: 74 g / 100 g). Resin M1 in a 500 ml autoclave equipped with a stirrer
00 g, cyclohexane 100 g, and nickel catalyst (N-113M, manufactured by Nikki Chemical Co., Ltd.) 3 g, hydrogenation reaction (60 kg / cm ² · G, 200 ° C., 3 hours) was performed, and the reaction product was cooled. After taking out and filtering to remove the catalyst, the solvent is removed by distillation to obtain a hydrogenated resin M (softening point: 1).
09 ° C, bromine number 1.6 g / 100 g, a / c: 0.022)
I got

Synthesis Example 14 Xylene (272 g) was charged into a 1-liter autoclave, heated to 260 ° C. in a nitrogen atmosphere, and a mixture of dicyclopentadiene (170 g) and styrene (170 g) was added over 2 hours while stirring. At the same temperature,
The reaction was further performed for 140 minutes. By removing unreacted substances and low-polymerized substances from the obtained polymer solution by distillation, the resin Q (styrene unit / DCPD unit weight ratio: 5
0/50, number average molecular weight: 610, softening point: 92 ° C., bromine value: 60 g / 100 g, aromatic ring content: 44% by weight)
I got In a 1 liter autoclave, add resin Q250
g, 3.0 g of a nickel-diatomaceous earth catalyst and 250 g of cyclohexane, and a hydrogenation reaction was carried out at a hydrogen pressure of 50 kg / cm ² · G and a temperature of 230 ° C. for 8 hours. The reaction product is cooled and taken out, filtered, and the catalyst is removed. Then, the solvent is removed by distillation to obtain a hydrogenated resin Q (softening point: 125 ° C., bromine value 2.2 g / 100 g, a / c: 0.037). , Aromatic ring content: 2.9% by weight, aromatic ring hydrogenation rate: 93%).

Synthesis Example 15 Xylene (228 g) was charged into a 1-liter autoclave, heated to 260 ° C. in a nitrogen atmosphere, and a mixture of 190 g of dicyclopentadiene and 190 g of styrene was added over 2 hours with stirring. At the same temperature,
The reaction was further performed for 4 hours. From the obtained polymer solution, unreacted substances and low-polymerized substances were removed by distillation to obtain a resin U (styrene unit / DCPD unit weight ratio: 50%).
/ 50, number average molecular weight: 690, softening point: 110 ° C., bromine value: 62 g / 100 g, aromatic ring content: 46% by weight)
I got In a 1 liter autoclave, add resin U250
g, 3.0 g of a nickel-diatomaceous earth catalyst and 250 g of cyclohexane, and a hydrogenation reaction was carried out at a hydrogen pressure of 40 kg / cm ² · G and a temperature of 230 ° C. for 5 hours. The reaction product was cooled and taken out, and after filtering to remove the catalyst, the solvent was removed by distillation to obtain a hydrogenated resin U (softening point: 125 ° C., bromine value: 4.4 g / 100 g, a / c: 0. 071, aromatic ring content: 24% by weight, aromatic ring hydrogenation rate: 48%).

Synthesis Example 16 First distillation 14 by-produced by naphtha steam cracking in a 500 ml flask equipped with a thermometer and a stirrer
A fraction at 0 ° C. and a final distillation of 200 ° C. (gas chromatographic analysis result, polymerizable component: 45% by weight: indene 2.5% by weight) 200
Then, 0.8 g of boron trifluoride-ether complex was added dropwise with stirring over 30 minutes while maintaining the temperature at 10 ° C. After the completion of the dropwise addition, stirring was continued at the same temperature for 4.5 hours. An aqueous sodium hydroxide solution was added to the obtained reaction mixture to remove the catalyst, followed by washing with water, followed by heating and drying to obtain resin Y (softening point: 118 ° C., bromine value 20 g / 100).
g) was obtained. Synthesis Example 17 AlCl _{3 in a} 1-liter stainless steel autoclave
Charge 1.3g, 20ml xylene, under stirring
Boiling point 25 to 10 in naphtha steam cracking
A mixture of 150 g of an aliphatic hydrocarbon fraction at 0 ° C and 50 g of xylene was added dropwise from a pressure-resistant cylinder over about 20 minutes while maintaining the reactor internal temperature at 60 ° C. After completion of the dropwise addition, stirring was continued at the same temperature for 3 hours. Methanol was added to the obtained reaction mixture to decompose the catalyst, washed with water, and then heated and dried to obtain resin Z (softening point: 103
° C, number average molecular weight: 480).

Examples 1-26 and Comparative Examples 1-4 Each raw material component was mixed in the composition shown in Table 1, kneaded in a Labo Plastomill at an internal temperature of 120 ° C, cooled, and then used in a feather mill. And coarsely pulverized. Next, after pulverizing with a jet mill, the particles were classified with an airflow classifier to obtain toner particles having a volume average particle diameter of 10 μm. At this time, the above kneaded material was fixed at a supply rate of 2.0 kg / hour, and the pulverization pressure was adjusted so that the volume average particle diameter became 10 μm by adjusting the pulverization pressure. To 100 parts by weight of the obtained toner particles, 0.5 parts by weight of titania fine particles (manufactured by Idemitsu Kosan Co., Ltd., Idemitsu Titania) was added and mixed with a Henschel mixer to obtain a toner for an electrostatic image phenomenon. . When evaluating this toner as a toner for a two-component developing system,
Idemitsu carrier (made by Idemitsu Kosan Co., Ltd .: polyethylene coated carrier) was used as the carrier. The toner particles and the toner were evaluated according to the following procedure. The results are shown in Table 2.

(1) Storage stability (blocking resistance) 10 g of toner particles were placed in a 100 ml beaker and kept in a constant temperature bath at 50 ° C. for 24 hours, and the state of aggregation was evaluated according to the following criteria. ◎: No aggregation or binding was observed. ：: Slight agglomeration was observed, but deagglomerated by shaking the beaker gently to restore fluidity. ×: Agglomerated and unable to deagglomerate (2) Low-temperature fixing property (minimum fixing temperature), offset resistance For measuring the minimum fixing temperature and offset occurrence temperature by modifying a commercial copying machine (Fuji Xerox “5039”) Test machine. The modification points are as follows. When evaluating the positively charged toner, an amorphous silicon photosensitive member was used, and when evaluating the negatively charged toner, an organic electrophotographic photosensitive member was used. -The temperature of the heat roll section of the fixing section is made variable, and the temperature of the fixing section can be measured. The photoconductor surface potential and the magnet roller bias potential were made variable. Using this tester, the minimum fixing temperature and offset occurrence temperature were measured.

(3) Toner Productivity (Pulverizability) In the step of pulverizing toner particles roughly pulverized by a feather mill with a jet mill, the pulverization pressure was measured, and the pulverizability was evaluated according to the following criteria. ◎: less than grinding pressure of 3.5kg / cm ² ○: grinding pressure of 3.5kg / cm ² more than 4.5kg / cm ²
Less than ×: Pulverization pressure of 4.5 kg / cm ² or more (4) Glass transition temperature (Tg) The glass transition temperature of the toner was measured in accordance with JIS K-7121, and the midpoint glass transition temperature in second heating was measured.

[0045]

[Table 1]

[0046]

[Table 2]

[Note] Elastomer: styrene-butadiene resin (softening point: 1)
45 ° C., Tg: 53 ° C.) “Priolite S-5B” manufactured by Goodyear Wax S: Fischer-Tropsch wax (falling melting point: 117 ° C., containing C38 to C93 components), “Paraflint C105” manufactured by Sasol Wax T: Fischer-Tropsch wax (falling melting point: 112 ° C., containing C28-C90 components), “Paraflint HI” manufactured by Sasol Other resin V: Polyester resin (softening point: 110 ° C., acid value: 5.0 mg KOH / g) Other resin W : Styrene-butyl acrylate copolymer resin (styrene unit / butyl acrylate unit weight ratio = 75
/ 25, weight average molecular weight 110000, Tg: 58 ° C) CCA: charge control agent, "Bontron S-34" (chromium-containing metal dye) manufactured by Orient Chemical Industries CB: carbon black, "MA-10 manufactured by Mitsubishi Chemical Corporation"
0 "

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

The toner binder resin for developing an electrostatic image of the present invention is a toner binder resin used for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. It is a resin and can provide a toner excellent in low-temperature fixing property, blocking resistance, tack resistance, toner pulverizability, and the like.

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

Claims (12)

[Claims] 1. A resin obtained by polymerizing at least one kind of monomer of cyclopentadiene, dicyclopentadiene and dihydrodicyclopentadiene, and (B) a part or a part of carbon-carbon unsaturated bonds of the resin. A toner binder resin for developing an electrostatic image, comprising at least one selected from all hydrogenated resins. 2. A copolymer resin obtained by polymerizing (A ′) at least one monomer of cyclopentadiene, dicyclopentadiene and dihydrodicyclopentadiene with another polymerizable monomer, wherein the polymerizable resin has another polymerizable property. (B ′) at least one selected from a resin obtained by hydrogenating a part or all of carbon-carbon unsaturated bonds and / or aromatic rings of the copolymer resin; A kind of toner binder resin for electrostatic image development. 3. The method according to claim 1, wherein the other polymerizable monomer has 8 to 13 carbon atoms.
3. The toner binder resin for developing an electrostatic image according to claim 2, which is at least one member selected from the group consisting of vinyl compounds containing an aromatic ring. 4. The polymerizable monomer is selected from α-methylstyrene, vinyltoluene, isopropenyltoluene, indene, alkyl-substituted indene, allylbenzene, allyltoluene, tert-butylstyrene and tert-butylallylbenzene. 4. The toner binder resin for developing an electrostatic image according to claim 3, which is at least one selected from the group consisting of: 5. The toner binder resin according to claim 3, wherein the other polymerizable monomer is styrene. 6. When the bromine value of the binder resin is a and the bromine value of the binder resin before hydrogenation is c, a / c
3. The toner binder resin for developing an electrostatic image according to claim 1, wherein the value is 0.45 or less. 4. 7. The toner binder resin for developing an electrostatic image according to claim 1, which is used for fixing with a heat roll. 8. A toner for developing an electrostatic image, comprising the binder resin according to claim 1 as a toner resin. 9. The electrostatic image developing toner according to claim 8, wherein the toner resin contains 70% by weight or more of the total amount of the binder resin according to claim 1. 10. The toner for developing an electrostatic image according to claim 8, wherein the toner resin further contains a wax. 11. The toner for developing electrostatic images according to claim 8, wherein the toner resin further contains an elastomer. 12. The electrostatic image developing toner according to claim 8, which is used for fixing with a heat roll.