WO2004107058A1 - トナー用バインダー樹脂および電子写真用トナー - Google Patents
トナー用バインダー樹脂および電子写真用トナー Download PDFInfo
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- WO2004107058A1 WO2004107058A1 PCT/JP2004/007663 JP2004007663W WO2004107058A1 WO 2004107058 A1 WO2004107058 A1 WO 2004107058A1 JP 2004007663 W JP2004007663 W JP 2004007663W WO 2004107058 A1 WO2004107058 A1 WO 2004107058A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08704—Polyalkenes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08793—Crosslinked polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
Definitions
- the present invention relates to a binder resin for a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, the present invention relates to an electrophotographic toner which can be used in a high-speed copying machine, and has high resolution, high image quality, and excellent crushability. Background art
- electrophotography in a PPC (P1ainPPerCopy) copier or printer is performed by the following method.
- the toner image is transferred onto a sheet to be fixed such as paper, and then fixed by heating with a hot roll.
- fixing is performed under heat and pressure, so that the method is quick and the heat efficiency is very good, and thus the fixing efficiency is very good.
- the heat roll method has good thermal efficiency, the toner contacts the heat roll surface in a molten state, causing toner to transfer to the heat roll surface and retransfer to the next sheet to be fixed.
- an offset prevention method for example, there is a method in which silicone oil is applied to the surface of a heat roll with a cloth or paper.
- the equipment becomes complicated, such as the necessity of installing a liquid supply device for offset prevention, which complicates repair and management, leading to increased costs, and contamination of the machine due to heat evaporation of silicon oil and the like due to heat.
- a new problem arises. For this reason, development of a toner for high-speed machines in a method that does not require the above-described application of silicone oil or the like (oilless fixing method) is desired.
- toners using a high molecular weight polymer or a crosslinked polymer have been proposed as an offset prevention method in the development of an oilless fixing toner.
- a method using a crosslinked polymer produced by an emulsion polymerization method such as Japanese Patent Publication No. 60-36582, or a suspension polymerization method, described in US Pat. No. 4,966,829.
- Methods using the prepared crosslinked polymers are disclosed. These methods have the advantage that a crosslinked polymer or high molecular weight polymer is easily obtained, but also use a dispersant or dispersing aid that easily absorbs moisture during production. Therefore, there is a problem that the electric characteristics, particularly the charge stability, are adversely affected, and it is not easy to remove them.
- toners with even better low-temperature fixability and excellent balance of fixability and offset resistance are used. It is an object of the present invention to provide a binder resin and a toner.
- the present inventors have conducted intensive studies to satisfy these requirements, and as a result, have found that In a binder resin for a toner obtained by subjecting a resin having a reactive group to a crosslinking reaction, a toner using a binder for a resin obtained by mixing a crosslinked resin having at least a specific amount of gel and a vinyl polymer.
- the first invention of the present application is obtained by reacting a crosslinking agent (A) with a vinyl polymer (B) satisfying the following requirements (I) to (III), and has a gel content of 1 to 50%.
- (I) It consists of a vinyl polymer (H) and a vinyl polymer (L), and the mass ratio (I ⁇ OZL) of both is 5/95 to 50/50.
- the vinyl polymer (H) has a weight-average molecular weight of more than 50 000 and 100 000 or less, and is selected from OH groups, COOH groups, acid anhydride groups and amino groups. The content of the group is 0.1 to 2 mol / kg of the vinyl polymer (H).
- the vinyl polymer (L) has a weight average molecular weight of 4,000 or more and 500,000 or less, and has a vinyl content of a functional group selected from an OH group, a COOH group, an acid anhydride group and an amino group. Polymer (L) Less than 0.7 mol / kg.
- a second invention of the present application is an electrophotographic toner including the above-mentioned binder resin for a toner.
- the binder resin for a toner according to the present invention comprises a crosslinking agent (A) and a vinyl polymer having a functional group selected from a hydroxyl group ( ⁇ H group), a hydroxyl group (COOH group), an acid anhydride group and an amino group. It is obtained by mixing the crosslinked resin (C) obtained from the union (B) and the vinyl polymer (D).
- the term “polymerization” may include the meaning of copolymerization, and the term “polymer” may include the meaning of a copolymer.
- the styrene-acrylic resin in the present invention is a copolymer of styrenes and (meth) acrylic acids and / or (meth) acrylates.
- the crosslinking agent (A) in the present invention is a functional group that reacts with the vinyl polymer (B) described below. There is no limitation as long as it has.
- the functional group which reacts with the vinyl polymer (B) is preferably an epoxy group.
- the crosslinking agent (A) is a glycidyl group-containing vinyl resin (A 1).
- the epoxy value of the glycidyl group-containing vinyl resin (A 1) is preferably in the range of 0.05 to 0.1 equivalent Z 100 g. When the epoxy value is within the above range, a gel is sufficiently formed, and the gel is not easily cut in the toner manufacturing process. Therefore, a toner having an offset resistance and a durable developing property can be obtained.
- the epoxy value means the number of g equivalents of epoxy groups contained in 100 g of the epoxy resin.
- the glycidyl group-containing vinyl resin (A 1) of the present invention can be obtained, for example, by polymerizing a monomer having a polymerizable double bond and a monomer having a glycidyl group and a polymerizable double bond. can get.
- styrenes As the monomer having a polymerizable double bond, styrenes, acrylates, methacrylates, unsaturated dibasic acid diesters, acrylonitrile, methacrylonitrile, amides and the like are preferable.
- styrenes As styrenes, styrene, p-methylstyrene, monomethylstyrene, vinyltoluene and the like are preferable.
- Acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, cyclohexyl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, and acrylic acid. Hydroxyethyl, hydroxybutyl acrylate, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate and the like are preferred.
- methacrylates examples include methyl methacrylate, methyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, and benzyl methacrylate.
- Preferred are furfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethylaminomethyl methacrylate, and dimethylaminoethyl methacrylate.
- Diesters of unsaturated dibasic acids include dialkyl fumarate, And alkyls.
- dialkyl fumarate dimethyl fumarate, dibutyl fumarate, dioctyl fumarate and the like are preferable.
- dialkyl maleate dimethyl maleate, dibutyl maleate, dioctyl maleate and the like are preferable.
- amides acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide and the like are preferable.
- particularly preferred vinyl monomers include styrenes, acrylates, methacrylates, dialkyl fumarate, acrylonitrile, acrylamide, methacrylamide and the like.
- the above compounds may be used in combination of two or more.
- specific examples of the monomer having a glycidyl group and a polymerizable double bond include glycidyl acrylate, j6 methyldaricidyl acrylate, glycidyl methacrylate, and i6 methyldaricidyl methacrylate. Particularly preferred are daricidyl methacrylate and i3-methyldaricidyl methacrylate.
- suspension polymerization As a method for polymerizing these compounds, suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and the like can be used without any particular limitation.
- bulk polymerization and solution polymerization which can be produced without using a dispersant or a dispersing agent are preferable.
- an aromatic hydrocarbon is preferable.
- the aromatic hydrocarbon include benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene, para-xylene, cumene and the like. These may be used alone or in combination. It is also possible to control the molecular weight using another solvent.
- the polymerization may be carried out using a polymerization initiator, or may be carried out using so-called thermal polymerization without using a polymerization initiator.
- the polymerization initiator is not particularly limited as long as it can be used as a radical polymerization initiator.
- azo initiators As the polymerization initiator, azo initiators, ketone peroxides, hydroxyketals, hide peroxides, dialkyl peroxides, diasyl peroxides, peroxide dicarbonates, sulfonyl are preferred. Examples include peroxysides and peroxyesters.
- azo-based initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2′-azobisisobutyrate, 1, -Azobis (1-cyclohexanecarbonitrile) and the like are preferred, and as the ketone peroxides, methylethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide and the like are preferred. As the hydroperoxides, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferable.
- hydridoxides t-butyl hydridoxide and the like are preferable.
- dialkyl peroxides examples include di-l-butyl peroxide, t-butyl cumyl peroxide, sicumyl peroxide, and 2,5-dimethyl-2,5-di (t-butyl veroxy). Xane and the like are preferred.
- isopyryl peroxide As the dioxides, isopyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide and the like are preferable.
- peroxydicarbonates examples include diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate and di-2-carbonate. Preference is given to ethoxyketyl peroxycarbonate.
- sulfonyl peroxides acetylcyclohexylsulfonyl peroxide and the like are preferable.
- peroxyesters examples include t-butyl peroxyacetate, t-butyl peroxy isobutyrate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, and the like. preferable. They can be used alone or in combination of two or more.
- the polymerization initiator used in the present invention can be appropriately selected and used depending on the type and amount of the monomer to be polymerized, the reaction temperature, the monomer concentration and the like.
- the amount used is preferably from 0.01 to 10 parts by mass per 100 parts by mass of the raw material monomer.
- the crosslinking agent (A) of the present invention is a crosslinking agent having a styrene acrylic resin structure in particular. Is preferred. Styrene acrylic resins have the advantage of being easy to control the polymerization reaction, being able to freely design physical properties, and being inexpensive.
- the Bier polymer (B) in the present invention comprises a vinyl polymer (H) and a vinyl polymer (L) described below.
- the Bier polymer (B) can be preferably obtained by separately producing the vinyl polymer (H) and the vinyl polymer (L) and mixing them.
- a method for producing the vinyl polymer (H) a method for producing by combining bulk polymerization and solution polymerization is preferable. Any conventionally known method can be employed for the bulk polymerization.
- the temperature during the reaction varies depending on the type of the monomer having a polymerizable double bond, but is preferably 90 ° C to 150 ° C, more preferably 100 ° C to 140 ° C. C range.
- the solution polymerization method any conventionally known method can be adopted.
- the temperature during the reaction varies depending on the types of the monomer having a polymerizable double bond, the polymerization initiator, and the solvent, but is preferably from 130 ° C to 210 ° C, more preferably from 14 ° C.
- Solution polymerization is preferred as a method for producing the vinyl polymer (L).
- the method of solution polymerization preferably, the method of solution polymerization described for the above-mentioned Bier polymer (H) is used.
- the vinyl polymer (B) in the present invention is preferably obtained by polymerizing the above compound having a polymerizable double bond. At this time, if necessary, it is possible to copolymerize with a monomer having a polymerizable double bond and a functional group selected from an OH group, a COOH group, an acid anhydride group and an amino group.
- the polymerization method and the polymerization conditions are the same as the above-mentioned method for producing the crosslinking agent (A).
- the monomer having a polymerizable double bond and a functional group selected from the group consisting of an OH group, a COH group, an acid anhydride group, and an amino group include the following compounds.
- Monomers having a COOH group or an acid anhydride group include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, keichic acid, monoesters of unsaturated dibasic acids, maleic anhydride, itaconic anhydride, etc. Is preferred.
- Monoesters of unsaturated dibasic acids include monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monooctyl fumarate, monomethyl maleate, monoethyl maleate Preferred are tyl, monopropyl maleate, monobutyl maleate, monooctyl maleate and the like.
- acrylic acid methacrylic acid, fumaric acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monooctyl fumarate, maleic anhydride, itaconic anhydride and the like.
- Examples of the monomer having an OH group include, for example, a monoester obtained from the above carboxylic acid or acid anhydride and a polyhydric alcohol.
- polyhydric alcohol examples include an alkyl diol, an alicyclic diol, an alkylene oxide adduct, and an aromatic diol.
- Alkyl diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butanediol, diethylene glycol, triethylene dalicol, Examples include dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, and 2-ethyl-1,3-hexanediol.
- Examples of the alicyclic diol include hydrogenated bisphenol A, cyclohexanedimethanol and the like.
- alkylene oxide adduct examples include reaction products of ethylene oxide, propylene oxide, and the like with bisphenol F and bisphenol S.
- aromatic diol examples include lower alcohol esters of carboxylic acids such as bishydroxybutyl terephthalic acid.
- esters of the above carboxylic acids and acid anhydrides with tri- or higher-valent polyols such as glycerin, 2-methylpropanetriol, trimethylolpropane, trimethylolethane, sorbit, and solpitan, and the like are also included.
- the amino group-containing monomer examples include N-methylamino (meth) acrylate, N-ethylamino (meth) acrylate, N-propinoamino (meth) acrylate, and N-butylamino (meth) acrylate.
- the vinyl polymer (H) of the present invention has a weight average molecular weight of more than 50,000 and not more than 100,000, preferably 100,000 to 700,000, more preferably 30,000 to 600,000 and an OH group, COOH group, acid anhydride group, amino group
- the content of the functional group selected from the group consisting of and 0.1 to 1 mol per kg of the resin is preferably 0.1 to 1 mol.
- the vinyl polymer (H) is preferably a component which mainly reacts with the crosslinking agent (A) to increase the molecular weight or to gel.
- the weight average molecular weight of the vinyl polymer (H) is within the above range, the vinyl polymer (H) reacts with the cross-linking agent (A) to easily increase the molecular weight or gel, and the resin after the reaction has It is preferable because the mechanical strength increases and the viscosity becomes high. Therefore, the obtained toner exhibits sufficient durability and offset resistance.
- the content of the functional group of the vinyl polymer (H) is within the above range, the resin after reacting with the crosslinking agent (A) has a preferable viscosity. Therefore, the obtained toner shows sufficient offset resistance, fixability, and pulverizability.
- the vinyl polymer (L) of the present invention has a weight average molecular weight of 4,000 to 50,000, preferably 5,000 to 30,000, more preferably 8,000 to 20,000, and an OH group, a COOH group, an acid anhydride group, an amino group,
- the content of the functional group selected from the group consisting of is less than 0.7 mol / kg, preferably less than 0.5 mol / kg, and more preferably less than 0.3 mol / kg of resin. That is, it is preferable that the vinyl polymer (L) hardly reacts with the crosslinking agent (A).
- the weight average molecular weight is within the above range, it is preferable in that a toner having good durability, offset resistance, fixability, and pulverizability can be obtained.
- the content of the functional group is within the above range, the low molecular weight component remains appropriately even after the reaction with the cross-linking agent (A), which is preferable in that sufficient fixability is exhibited.
- the vinyl polymer (B) of the present invention preferably has a styrene acrylic resin structure from the viewpoints of reaction control, flexibility in designing physical properties, cost and the like.
- the number average molecular weight and weight average molecular weight in the present invention are determined by gel permeation chromatography (GPC), and are converted molecular weights based on a calibration curve prepared with monodispersed standard polystyrene.
- the measurement conditions are as follows.
- Sample concentration 0.002 g-resin / ml-THF (Used by filtering through a membrane filter just before measurement to remove insoluble parts, dust, etc.)
- the binder resin for toner of the present invention is obtained by mixing a crosslinked resin (C) containing a gel component obtained from a crosslinker (A) and a vinyl polymer (B) with a vinyl polymer (D). Containing resin.
- a crosslinked resin (C) containing a gel component obtained from a crosslinker (A) and a vinyl polymer (B) with a vinyl polymer (D). Containing resin.
- the beer polymer (D) any vinyl polymer which is conventionally used as a binder resin for a toner can be used without limitation.
- it is a styrene-based copolymer or a (meth) acrylic acid (ester) -based copolymer, preferably a so-called styrene-acrylic resin.
- Other preferred examples include the above-mentioned vinyl polymer (B).
- a method of reacting the crosslinking agent (A) with the vinyl polymer (B) a method of reacting the crosslinking agent (A) with the vinyl polymer (B) by melt-mixing is preferable.
- the method of heating and melting any conventionally known method can be employed, but a method using a twin-screw mixer is particularly preferable.
- the vinyl polymer (B) and the crosslinking agent (A) are mixed with a Henschel mixer or the like, and then reacted while being melt-kneaded using a biaxial kneader.
- the temperature during the reaction varies depending on the type of the crosslinking agent (A) or the vinyl polymer (B), but is preferably from 100 ° C to 240 ° C, preferably from 150 ° C to 220 ° C. Range.
- a reaction vessel equipped with a stirrer can be used.
- the crosslinked resin (C) of the present invention has a gel component.
- the content (gel content (%;)) of the gel component in the crosslinked resin (C) is 1% by mass to 50% by mass, preferably 3% by mass to 35% by mass, more preferably 5% by mass. % Or more and 30% by mass or less.
- a gel means an ethyl acetate-insoluble content in a resin.
- the content of the gel component in the present invention is a value measured as follows. Add 2.5 g of resin and 47.5 g of ethyl acetate to a 100 ml sample tube.
- This sample tube is stirred at a rotation speed of 50 rpm at 22 ° C for 12 hours, and then left at 22 ° C for 12 hours. After standing, 5 g of the supernatant of the sample tube is dried at 150 ° C for 1 hour, weigh (Xg), and calculate according to the following formula.
- the mass ratio (C) (D) of the crosslinked resin (C) to the vinyl polymer (D) is preferably 20/80 to 80/20. Particularly preferably, (C) / (D) is 40 to 60/40.
- the mass ratio (C) Z (D) of the crosslinked resin (C) to the vinyl polymer (D) is 80/20 to 90Z10, and the weight average molecular weight of the vinyl polymer (D) is 4000 As described above, the vinyl polymer (D1) having a molecular weight of 50,000 or less is also preferable.
- the content of the cross-linked resin (C) be within the above range, since the binder resin has an appropriate gel component and exhibits sufficient offset resistance and fixability.
- the weight average molecular weight of the vinyl polymer (D1) is more preferably 4,000 or more and 30 000 or less, and particularly preferably 4,000 or more and 20,000 or less.
- a toner having good durability, offset resistance, fixability, and pulverizability can be obtained.
- Moderate mechanical strength and viscosity of the resin can be achieved.
- any conventionally known method can be employed, but a method using a single blender for mixing powder is preferred.
- the crosslinked resin (C) and the vinyl polymer (D) there is a method of mixing the crosslinked resin (C) and the vinyl polymer (D) with a Henschel mixer for 2 minutes.
- melt mixing or the like can be used in addition to the method using one blender.
- a preferred example is a method using a known single-screw or twin-screw extruder.
- the vinyl polymer (D) and the crosslinked resin (C) are mixed with a Henschel mixer or the like as described above, but also a high level It is possible to obtain a binder resin for toner having a balance between fixability and offset resistance.
- the resin thus obtained is cooled and pulverized to obtain a binder resin for a toner.
- a method of cooling and pulverizing any conventionally known method can be employed, but as a cooling method, rapid cooling using a steel belt cooler or the like is also possible.
- the electrophotographic toner of the present invention contains the binder resin of the present invention as a necessary component.
- Components other than the binder resin include a colorant, a charge control agent, a release agent, and a pigment dispersant.
- Coloring agents include, for example, black pigments such as carbon black, acetylene black, lamp black, magnetite, etc. Dunslen, Brilliant Orange GK, Bengala, Brilliant Power—Min 6B, Frizarin Lake, Methyl Violet Lake, Fast Violet B, Cobalt Blue, Alkaline Bull Lake, Phthalocyanine Blue, First Sky Sky Blue, Pigment Green B, Malachite Green Known organic pigments such as lake, titanium oxide and zinc white are exemplified. The amount is preferably 5 to 250 parts by mass with respect to 100 parts by mass of the binder resin for toner.
- polyvinyl chloride polyvinyl acetate, polyolefin, polyester, polyvinyl butyral, polyurethane, polyamide, rosin, modified rosin, terpene resin, phenol resin, Aliphatic hydrocarbon resin, aromatic petroleum resin, paraffin wax, polyolefin wax, fatty acid amide wax, vinyl chloride resin, styrene-butadiene resin, chroman-indene resin, melamine resin and the like may be partially used.
- the amount is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the binder resin for toner.
- charge control agents such as Nigguchi Shin, quaternary ammonium salts and metal-containing azo dyes can be appropriately selected and used.
- the amount used is 1 for binder resin for toner. It is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass.
- any conventionally known method can be employed as a method for producing an electrophotographic toner. For example, after pre-mixing a binder resin for toner, a colorant, a charge control agent, a box, etc., kneading the mixture in a heated and melted state using a biaxial kneader, and after cooling, pulverize using a pulverizer.
- the particles are classified by a pneumatic classifier, and usually particles in the range of 8 to 20 can be collected to obtain an electrophotographic toner.
- the resin temperature at the discharge section of the twin-screw mixer is less than 165 ° C and the residence time is less than 180 seconds.
- a cooling method rapid cooling using a steel belt cooler or the like is preferable.
- the toner for electrophotography obtained as described above contains the binder resin for toner of the present invention preferably at least 50% by mass, more preferably at least 60% by mass.
- the upper limit is preferably 99% by mass.
- parts means “parts by mass” unless otherwise specified.
- a crosslinker A-2 was obtained in exactly the same manner as in Production Example A-1, except that glycidyl methacrylate was changed to 0.65 parts in Production Example A-1.
- Table 3 shows the physical property values of the obtained product.
- a cross-linking agent A-3 was obtained in exactly the same manner as in Production Example A-1, except that dalicidyl methacrylate was changed to 13 parts in Production Example A-1. Physical properties of the obtained product are shown in Table 4.
- LS low molecular weight polymerization solution
- a vinyl polymer B-9 was obtained in exactly the same manner as in B-1 except that 16 parts of the high molecular weight polymerization liquid (HS) and 16 parts of the low molecular weight polymerization liquid (LS) were used in Production Example B-1. .
- Table 2 shows the physical property values of the obtained product.
- a vinyl polymer B-10 was obtained in exactly the same manner as in B-1 except that 116 parts of the high molecular weight polymerization liquid (HS) and 88 parts of the low molecular weight polymerization liquid (LS) were used in Production Example B-1. Was. Table 2 shows the physical property values of the obtained product.
- Production example B—1 3 When producing a low molecular weight polymerization solution (LS) in Production Example B-1, 82 parts of styrene, 17 parts of n-butyl acrylate, and 1.0 part of methacrylic acid were mixed with 76.8 parts of styrene and n-acrylic acid. -A vinyl polymer B-13 was obtained in exactly the same manner as B-1, except that 17 parts of butyl and 6.2 parts of methacrylic acid were used. Table 5 shows the physical property values of the obtained product.
- LS low molecular weight polymerization solution
- Production example B-17 A vinyl polymer B-17 was obtained in exactly the same manner as in Preparation Example B-1, except that 10 parts of the high molecular weight polymerization solution (HS) and 170 parts of the low molecular weight polymerization solution (LS) were used. Table 6 shows the physical property values of the obtained product.
- a vinyl polymer B_18 was obtained in exactly the same manner as in B-1 except that 183 parts of the high molecular weight polymerization solution (HS) and 79 parts of the low molecular weight polymerization solution (LS) were used in Production Example B_1.
- Table 6 shows the physical property values of the obtained product.
- a crosslinked resin C-2 ⁇ (: 124) was obtained in the same manner as in Production Example C-11, except that the types and amounts of the crosslinking agent and the vinyl polymer were changed to the conditions shown in Tables 1 to 6.
- the obtained resin Table 1 to Table 6 also show the physical property values of
- a mixture of 50 parts of the crosslinked resin C-1 and 50 parts of the vinyl polymer B-1 in a Henschel mixer for 2 minutes was used as a binder resin for toner. After that, add 8 parts of car pump rack MA100 (Mitsubishi Kasei), 5 parts of polypropylene wax (Viscol 550P), and 1 part of Aizenspiron Black TRH as a charge control agent, and then add the shell shell mixer again. After kneading, the mixture was kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Kikai) at a resin temperature of 150 ° C at the discharge part of the twin-screw mixer and a residence time of 30 seconds.
- PCM-30 type manufactured by Ikegai Kikai
- Table 1 shows the results obtained by mixing 3 parts of this toner and 97 parts of Carrier to make a developer, modifying a commercial high-speed copying machine, writing an image, and evaluating the image.
- a binder resin for toner and a toner were obtained in the same manner as in Example 1 except that the types and amounts of the crosslinked resin and the vinyl polymer were set to the conditions shown in Tables 1 to 6, and the performance was evaluated.
- Tables 1 to 4 show the results of the examples, and Tables 5 to 6 show the results of the comparative examples. Evaluation method for toner
- the evaluation was performed at the temperature of the fixing roll where an offset occurs when copying is performed. ⁇ ; 230 ° C or more
- ⁇ 50% or more and less than 70%
- Line width increase 0 (line width of copy paper) one (line width of base paper)
- THF insoluble matter (mass%) 10.8 10 21 5 22 Vinyl polymer (L) Weight average molecular weight 12000 12000 12000 12000 12000 Vinyl polymer (L) Functional group content (mol / Kg) 0.12 0.12 0.12 0.12 0.12 0.12 Vinyl polymer ( H) Weight average molecular weight 55000 300000 300000 300000 300000 Vinyl polymer (H) Functional group content (mol / Kg) 0.27 0.12 1.9 0.27 0.27 Weight ratio (H / L) 30/70 30/70 30/70 5/95 50 / 50 Vinyl resin (D) B-6 B-7 B-8 B-9 B-10 Weight average molecular weight (D)
- THF insoluble matter (% by mass) 7 15 15 15 15
- Vinyl polymer (L) Weight average molecular weight 12000 12000 12000 12000 Vinyl polymer (L) Functional group content (mol / Kg) 0.12 0.12 0.12 0.12 Vinyl polymer (H) weight Average molecular weight 300000 300000 300000 300000 Vinyl polymer (H) functional group content (mol / Kg) 0.27 0.27 0.27 0.27 Weight ratio (H / L) 30/70 40/60 40/60 40/60 Vinyl resin (D) B -1 B-19 B-20 B-19 Weight average molecular weight (D) 150000 4000 50000 4000 Weight ratio (C / D) 50/50 80/20 80/20 90/10 Fixing property O ⁇ ⁇ ⁇ Offset property ⁇ ⁇ ⁇ ⁇ Crushability ⁇ ⁇ ⁇ ⁇ Durability ⁇ o O o Five
- the present inventors specified the respective molecular weights, functional group contents and ratios of the vinyl polymer (H) and the vinyl polymer (L), and determined the amount of gel produced.
- a binder resin for toner with better low-temperature fixability and excellent offset resistance can be obtained.
- the toner using the binder resin for a toner of the present invention has excellent pulverizability and durable developing property, and has practically excellent performance.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04735132A EP1630620A4 (en) | 2003-05-29 | 2004-05-27 | BINDER RESIN FOR TONERS AND TONERS FOR ELECTROPHOTOGRAPHY |
US10/554,146 US20060251980A1 (en) | 2003-05-29 | 2004-05-27 | Binder resin for toner and toner for electrophotography |
JP2005506555A JPWO2004107058A1 (ja) | 2003-05-29 | 2004-05-27 | トナー用バインダー樹脂および電子写真用トナー |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-153550 | 2003-05-29 | ||
JP2003153550 | 2003-05-29 |
Publications (1)
Publication Number | Publication Date |
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WO2004107058A1 true WO2004107058A1 (ja) | 2004-12-09 |
Family
ID=33487297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/007663 WO2004107058A1 (ja) | 2003-05-29 | 2004-05-27 | トナー用バインダー樹脂および電子写真用トナー |
Country Status (7)
Country | Link |
---|---|
US (1) | US20060251980A1 (ja) |
EP (1) | EP1630620A4 (ja) |
JP (1) | JPWO2004107058A1 (ja) |
KR (1) | KR100676272B1 (ja) |
CN (1) | CN100383669C (ja) |
TW (1) | TWI243973B (ja) |
WO (1) | WO2004107058A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007052274A (ja) * | 2005-08-18 | 2007-03-01 | Sharp Corp | トナーおよびその製造方法 |
KR101032223B1 (ko) * | 2006-11-29 | 2011-05-02 | 미쓰이 가가쿠 가부시키가이샤 | 토너용 수지 조성물 및 그 수지 조성물을 이용한 토너 |
US10088765B2 (en) * | 2016-10-17 | 2018-10-02 | Canon Kabushiki Kaisha | Toner and method for producing toner |
Citations (6)
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JPS61163347A (ja) * | 1985-01-16 | 1986-07-24 | Hitachi Chem Co Ltd | 電子写真用トナ− |
JPH0611890A (ja) * | 1992-01-31 | 1994-01-21 | Mitsui Toatsu Chem Inc | 電子写真用トナー及びその製造法 |
JPH09244295A (ja) * | 1996-03-05 | 1997-09-19 | Sekisui Chem Co Ltd | トナー用樹脂組成物及びトナー |
JP2001188383A (ja) * | 1999-12-28 | 2001-07-10 | Canon Inc | 乾式トナー |
JP2002221813A (ja) * | 2000-11-07 | 2002-08-09 | Canon Inc | トナー、画像形成装置、プロセスカートリッジ及び画像形成方法 |
JP2003241427A (ja) * | 2002-02-19 | 2003-08-27 | Canon Inc | トナー |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6036582B2 (ja) * | 1979-05-08 | 1985-08-21 | キヤノン株式会社 | 現像用トナ− |
CA2088093C (en) * | 1992-01-31 | 1999-06-29 | Masaaki Shin | Electrophotographic toner and production process thereof |
CA2098233C (en) * | 1992-06-19 | 1999-06-29 | Kazuyoshi Hagiwara | Toner for developing electrostatic image and image forming method |
JP3066020B2 (ja) * | 1998-07-03 | 2000-07-17 | 三洋化成工業株式会社 | 電子写真用トナ―バインダ― |
JP2002023417A (ja) * | 2000-07-03 | 2002-01-23 | Canon Inc | トナー、画像形成方法及び画像形成装置 |
US6537715B2 (en) * | 2000-07-28 | 2003-03-25 | Canon Kabushiki Kaisha | Toner, image-forming method and process cartridge |
TWI227384B (en) * | 2000-10-12 | 2005-02-01 | Mitsui Chemicals Inc | A toner binder for electrophotography and toner for electrophotography |
US6670087B2 (en) * | 2000-11-07 | 2003-12-30 | Canon Kabushiki Kaisha | Toner, image-forming apparatus, process cartridge and image forming method |
CN100492188C (zh) * | 2002-08-08 | 2009-05-27 | 三井化学株式会社 | 调色剂用粘结剂树脂和调色剂 |
-
2004
- 2004-05-27 EP EP04735132A patent/EP1630620A4/en not_active Withdrawn
- 2004-05-27 TW TW093115079A patent/TWI243973B/zh active
- 2004-05-27 WO PCT/JP2004/007663 patent/WO2004107058A1/ja active Application Filing
- 2004-05-27 KR KR1020057022169A patent/KR100676272B1/ko active IP Right Grant
- 2004-05-27 JP JP2005506555A patent/JPWO2004107058A1/ja active Pending
- 2004-05-27 CN CNB2004800145842A patent/CN100383669C/zh not_active Expired - Lifetime
- 2004-05-27 US US10/554,146 patent/US20060251980A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61163347A (ja) * | 1985-01-16 | 1986-07-24 | Hitachi Chem Co Ltd | 電子写真用トナ− |
JPH0611890A (ja) * | 1992-01-31 | 1994-01-21 | Mitsui Toatsu Chem Inc | 電子写真用トナー及びその製造法 |
JPH09244295A (ja) * | 1996-03-05 | 1997-09-19 | Sekisui Chem Co Ltd | トナー用樹脂組成物及びトナー |
JP2001188383A (ja) * | 1999-12-28 | 2001-07-10 | Canon Inc | 乾式トナー |
JP2002221813A (ja) * | 2000-11-07 | 2002-08-09 | Canon Inc | トナー、画像形成装置、プロセスカートリッジ及び画像形成方法 |
JP2003241427A (ja) * | 2002-02-19 | 2003-08-27 | Canon Inc | トナー |
Non-Patent Citations (1)
Title |
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See also references of EP1630620A4 * |
Also Published As
Publication number | Publication date |
---|---|
JPWO2004107058A1 (ja) | 2006-07-20 |
TWI243973B (en) | 2005-11-21 |
CN100383669C (zh) | 2008-04-23 |
KR100676272B1 (ko) | 2007-02-02 |
KR20060015279A (ko) | 2006-02-16 |
EP1630620A1 (en) | 2006-03-01 |
TW200506556A (en) | 2005-02-16 |
CN1795419A (zh) | 2006-06-28 |
US20060251980A1 (en) | 2006-11-09 |
EP1630620A4 (en) | 2008-12-24 |
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