Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
• • 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
  • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08755—Polyesters
• • 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
  • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a toner binder and a toner to be used for electrophotography, electrostatic recording, electrostatic printing, and so on.
• a toner binder for electrophotography for a heat fixing system which is a fixing system of images commonly applied in copiers, printers and the like, is required to allow a toner not to fuse to a hot roller even at a high fixing temperature (hot offset resistance), to be capable of fixing a toner even at a low fixing temperature (low-temperature fixing property), to have storage stability as microparticles (blocking resistance), and the like.
• Patent Document 1 In order to improve such fixing performances of a toner, it is conventionally known to use incompatible resins specialized in a low temperature range and a high temperature range as a matrix phase and a domain phase, respectively.
• a compatibilizing agent for compatibilizing the incompatible resins is contained in a vinyl resin such as a styrene type polymer (Patent Document 1 and the like).
• toner binder composed of a polyester resin obtained by using a specific polyol component such as 1,2-propylene glycol and neopentyl glycol, without consideration for the SP value range and the HLB value range (Patent Document 2 and the like).
• toners composed of a matrix phase and a domain phase do not sufficiently satisfy all of fixing properties (balance between low-temperature fixing property and hot offset resistance) and storage stability, and they are requested to have a particularly wide fixing temperature range when recent high-speed machines or small electronic copiers are used.
• An object of the present invention is to provide a toner binder and a toner, wherein the toner binder, when used in a toner, can ensure a widened fixing temperature range, excellent blocking resistance under high-temperature and -humidity conditions, and excellent electrification characteristics.
• the present invention includes the following two inventions.
• a toner binder which contains a polyester resin (P) composed of two or more polyester resins that are each obtained by polycondensation of a carboxylic acid component (x) and an alcohol component (y), wherein the alcohol component (y) of at least one (P1) constituting the (P) contains 30 to 100 molar % of an adduct (y1) of bisphenol A with 2 to 4 ethylene oxide molecules, the alcohol component (y) of at least one (P2) constituting the (P) contains 50 to 95 molar % of an aliphatic diol (y2) having 2 to 4 carbon atoms, the (P2) is other than the (P1), and the (P) satisfies relationships (1) and (2),
• a toner which contains the above-mentioned toner binder, a colorant and, as necessary, one or more additives selected from a release agent, a charge controlling agent and a fluidizer.
• toner binder of the present invention has made it possible to provide a toner which can ensure a widened fixing temperature range, excellent blocking resistance under high-temperature and -humidity conditions, and excellent electrification characteristics (saturated electrification amount, rise of electrification, electrification stability).
• the toner binder of the present invention contains a polyester resin (P) composed of two or more polyester resins that are each obtained by polycondensation of a carboxylic acid component (x) and an alcohol component (y).
• the polyester resin (P) is required to satisfy the following: the alcohol component (y) of at least one (P1) constituting the (P) contains 30 to 100 molar % of an adduct (y1) of bisphenol A with 2 to 4 ethylene oxide (hereinafter abbreviated as EO) molecules, the alcohol component (y) of at least one (P2) constituting the (P) contains 50 to 95 molar % of an aliphatic diol (y2) having 2 to 4 carbon atoms, and the (P2) is one other than the (P1) [namely, one not containing 30 to 100 molar % of the (y1) in the (y)].
• the (P1) and the (P2) each may be used in a combination of two or more thereof.
• the polyester resin (P) is preferably composed of a linear polyester resin (A) and a nonlinear polyester resin (B).
• the (A) and the (B) each may be used in a combination of two or more thereof.
• the polyester resin (P) is composed of the linear polyester resin (A) and the nonlinear polyester resin (B), the (A) and/or the (B) is required to contain the (P1) and the (A) and/or the (B) is required to contain the (P2).
• the (A) be the (P1) and it is more preferable that the (B) be the (P2).
• a linear polyester resin (A) that corresponds to the (P1) containing 30 to 100 molar % of the adduct (y1) of bisphenol A with 2 to 4 EO molecules in the alcohol component (y) may be denoted by a linear polyester resin [P1(A)]
• a nonlinear polyester resin (B) that corresponds to the (P1) may be denoted by a nonlinear polyester resin [P1(B)]
• a linear polyester resin (A) that corresponds to the (P2) containing 50 to 95 molar % of the aliphatic diol (y2) having 2 to 4 carbon atoms in the alcohol component (y) may be denoted by a linear polyester resin [P2(A)]
• a nonlinear polyester resin (B) that corresponds to the (P2) may be denoted by a nonlinear polyester resin [P2(B)].
• Examples of the alcohol component (y) that constitutes the linear polyester resin (A) include diols, tri- to octa- or higher hydric polyols, and monools.
• diols examples include aliphatic diols (y2) having 2 to 4 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, and the like), aliphatic diols having 5 to 36 carbon atoms (neopentyl glycol, 2,3-dimethylbutane-1,4-diol, 1,6-hexanediol, 1,8-octanediol, and the like); alkylene ether glycols having 5 to 36 carbon atoms (triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and the like); (poly)oxyalkylene [the
• polyoxyalkylene ethers (the number of AO units is 2 to 30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, and the like), more preferred is the adduct (y1) of bisphenol A with 2 to 4 EO molecules, and particularly preferred is an 85% or more adduct (y11) of bisphenol A with 2 EO molecules.
• tri- to octa- or higher hydric polyols examples include aliphatic tri- to octa- or higher polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and their intramolecular or intermolecular dehydration products, e.g., glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerol, and dipentaerythritol; saccharides and derivatives thereof, e.g., sucrose and methyl glucoside); (poly)oxyalkylene ethers (the number of AO unit(s) is 1 to 30) of the above-mentioned aliphatic polyhydric alcohols; polyoxyalkylene ethers (the number of AO units is 2 to 30) of trisphenols (trisphenol PA and the like); and polyoxyalkylene ethers (the number of AO
• Preferred among such tri- to octa- or higher hydric polyols are polyoxyalkylene ethers (the number of AO units is 2 to 30) of novolac resins.
• Examples of the monools include alkanols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and the like).
• alkanols having 8 to 24 carbon atoms
• dodecyl alcohol, myristyl alcohol, stearyl alcohol, and combinations thereof are more preferred.
• examples of the alcohol component (y) that constitutes the [P1(A)] include, in addition to the essential adduct (y1) of bisphenol A with 2 to 4 EO molecules, diols other than the (y1), tri- to octa- or higher hydric polyols, and monools.
• a commercially available adduct of bisphenol A with 2 to 4 EO molecules contains unreacted bisphenol A, an adduct with one EO molecule and an adduct with 5 or more EO molecules in a small amount as impurities in addition to an adduct with 2 to 4 EO molecules.
• the adduct (y1) of bisphenol A with 2 to 4 EO molecules is defined as one that contains an adduct with 2 to 4 EO molecules in 80% or more relative to the whole of the adducts with EO (including unreacted bisphenol A, an adduct with one EO molecule, adducts with 2 to 4 EO molecules and adducts with 5 or more EO molecules) as measured by the method described below.
• an adduct of bisphenol A with 2 EO molecules is defined as one that contains an adduct with 2 EO molecules in 60% or more relative to the whole of the adducts with EO (including unreacted bisphenol A, an adduct with one EO molecule, an adduct with 2 EO molecules, and adducts with 3 or more EO molecules) as measured by the method described below
• an adduct of bisphenol A with 3 EO molecules is defined as one that contains an adduct with 3 EO molecules in 60% or more relative to the whole of the adducts with EO (including unreacted bisphenol A, adducts with 1 to 2 EO molecules, an adduct with 3 EO molecules, and adducts with 4 or more EO molecules) as measured by the method described below.
• the adduct of bisphenol A with 2 EO molecules, the adduct with 3 EO molecules, and the adduct with 4 EO molecules usually satisfy also the definition of the above-mentioned adduct (y1) of bisphenol A with 2 to 4 EO molecules, they correspond to the (y1).
• the purity thereof is preferably 85% or more, more preferably 90% or more in terms of storage stability.
• the content of the adduct of bisphenol A with one EO molecule in the adduct (y1) of bisphenol A with 2 to 4 EO molecules is preferably 1.5% or less, more preferably 1.2% or less.
• the content of the adduct of bisphenol A with 2 to 4 EO molecules in the adducts of bisphenol A with EO in the present invention, the purity of the adduct (y11) of bisphenol A with 2 EO molecules, and the content of the adduct of bisphenol A with one EO molecule in the adduct (y1) of bisphenol A with 2 to 4 EO molecules are values determined by the methods described below.
• TMSI-H silylation agent
• a silylation agent [TMSI-H, produced by GL Sciences, Inc.] is added to 30 to 50 mg of a sample (an adduct of bisphenol A with EO), which is dissolved in a hot water bath (50 to 70° C.), followed by vibration for 2 minutes to perform silylation.
• the mixture is left at rest for separation, followed by gas chromatography analysis of the supernatant liquid to measure the peak areas of unreacted bisphenol A, an adduct with one EO molecule, an adduct with 2 EO molecules, an adduct with 3 EO molecules, an adduct with 4 EO molecules, and an adduct with 5 EO molecules.
• the area of the adduct with 2 EO molecules, the adduct with 3 EO molecules and the adduct with 4 EO molecules in the total peak area, expressed in percentage, is taken as the content of the adduct of bisphenol A with 2 to 4 EO molecules.
• the area of the adduct with 2 EO molecules in the total peak area, expressed in percentage, is taken as the purity of the adduct of bisphenol A with 2 EO molecules.
• the area of the adduct with one EO molecule in the total peak area, expressed in percentage, is taken as the content of the adduct of bisphenol A with one EO molecule in the adduct (y1) of bisphenol A with 2 to 4 EO molecules. No unreacted bisphenol A or no adduct with 6 or more EO molecules existed in the adducts of bisphenol A with 2 to 4 EO molecules used in Example and Comparative Examples of the present invention.
• Carrier gas helium
• Air pressure 0.5 kg/cm 2
• the content of the adduct (y1) of bisphenol A with 2 to 4 EO molecules in the alcohol component (y) of the linear polyester resin [P1(A)] is usually 30 to 100 molar %, preferably 50 to 100 molar % in terms of fixing property.
• examples of the alcohol component (y) that constitutes the [P2(A)] include, in addition to the essential aliphatic diol (y2) having 2 to 4 carbon atoms, diols other than the (y2), tri- to octa- or higher hydric polyols, and monools.
• Examples of the aliphatic diol (y2) having 2 to 4 carbon atoms include those mentioned above, and two or more thereof may be used in combination.
• y2 Preferred among these (y2) are ethylene glycol and 1,2-propylene glycol, and ethylene glycol is more preferred.
• the linear polyester resin (A) [hereinafter means both [P1(A)] and [P2(A)]] preferably contains at least one of a monool and the monocarboxylic acid (x1) mentioned below in the carboxylic acid component (x) and/or the alcohol component (y), and more preferably contains the monocarboxylic acid (x1) in the carboxylic acid component (x).
• a monool When a monool is contained, it is preferably used in such an amount (calculated value) that 5 molar % or more, more preferably 6 to 85 molar %, particularly preferably 8 to 80 molar %, most preferably 10 to 76 molar %, of the terminal carboxyl groups of the (A) are esterified with the monool in terms of storage stability and production efficiency.
• the carboxylic acid component (x) that constitutes the linear polyester resin (A) is preferably composed of a polycarboxylic acid (x2) and, as necessary, a monocarboxylic acid (x1), and is more preferably composed of a monocarboxylic acid (x1) and a polycarboxylic acid (x2).
• examples of the aliphatic (including alicyclic) monocarboxylic acid include alkane monocarboxylic acids having 1 to 30 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, and the like), and alkene monocarboxylic acids having 3 to 24 carbon atoms (acrylic acid, methacrylic acid, oleic acid, linoleic acid, and the like).
• examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, p-t-butylbenzoic acid, phenylpropionic acid, naphthoic acid, and the like).
• (x1) aromatic monocarboxylic acids having 7 to 36 carbon atoms; benzoic acid, methylbenzoic acid, and p-t-butylbenzoic acid are more preferred, and benzoic acid is particularly preferred.
• the monocarboxylic acid (x1) is used in the linear polyester resin (A), it is preferably used in such an amount (calculated value) that 5 molar % or more, more preferably 6 to 85 molar %, particularly preferably 8 to 80 molar %, most preferably 10 to 76 molar %, of the terminal hydroxyl groups of the (A) are esterified with the (x1) in terms of storage stability and production efficiency.
• the amount of the monocarboxylic acid (x1) in the constitutional units of the linear polyester resin (A) is preferably 30 molar % or less, more preferably 1 to 25 molar %, and particularly preferably 2 to 21 molar % relative to the whole carboxylic acid component (x).
• polycarboxylic acid (x2) examples include a dicarboxylic acid (x21) and/or a tri- to hexa- or higher valent polycarboxylic acid (x22).
• dicarboxylic acid (x21) examples include alkane dicarboxylic acids having 4 to 36 carbon atoms (e.g., succinic acid, adipic acid, and sebacic acid); alicyclic dicarboxylic acids having 6 to 40 carbon atoms [e.g., dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acids having 4 to 36 carbon atoms (e.g., alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and the like); and ester-forming derivatives thereof [lower alkyl (the number of carbon atoms of alkyl: 1 to 4; methyl, ethyl,
• alkene dicarboxylic acids having 4 to 20 carbon atoms aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof, and terephthalic acid, isophthalic acid, and/or lower alkyl (the number of carbon atoms of alkyl: 1 to 4) esters thereof (x211) are more preferred.
• Examples of the tri- to hexa- or higher valent polycarboxylic acid (x22) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like), aliphatic polycarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid and the like), and ester-forming derivatives thereof, and two or more thereof may be used in combination.
• trimellitic acid pyromellitic acid
• ester-forming derivatives thereof Preferred among these are trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof.
• the content of terephthalic acid, isophthalic acid, and/or lower alkyl (the number of carbon atoms of alkyl: 1 to 4) esters thereof (x211) in the polycarboxylic acid (x2) is preferably 85 to 100 molar %, and more preferably 90 to 100 molar % in terms of storage stability.
• the molar ratio of the terephthalic acid and/or the lower alkyl ester thereof to the isophthalic acid and/or the lower alkyl ester thereof in the (x211) is preferably from 20:80 to 100:0, and more preferably from 30:70 to 100:0 in terms of the mechanical strength of resin.
• the content of the aromatic carboxylic acid in the carboxylic acid component (x) of the linear polyester resin (A) is preferably 80 to 100 molar %, and more preferably 85 to 100 molar % in terms of storage stability and fixing property.
• the percentage of the total of the tri- to octa- or higher hydric polyols and the tri- to hexa- or higher valent polycarboxylic acids (x22) in the total of the carboxylic acid component (x) and the alcohol component (y) is preferably 0.1 to 15 molar %, and more preferably 0.2 to 12 molar %.
• the percentage is 0.1 molar % or more, the storage stability of a toner is good, whereas when it is 15 molar % or less, the electrification characteristics of a toner are good.
• the method for producing a linear polyester resin (A) by polycondensation of a carboxylic acid component (x) composed of a polycarboxylic acid (x2) and, as necessary, a monocarboxylic acid (x1) as well as an alcohol component (y) is not particularly limited and, for example, a mixture of the (x1) and (x2) and the (y) can also be polycondensed at once, at least part of the (x2) and the (y) may be polycondensed beforehand in such an equivalent ratio that the hydroxyl groups of the (y) are excessive, then the hydroxyl groups of the resulting polycondensate (A0) may be reacted with the carboxyl groups of the (x1), and further polycondensed.
• a tri- to hexa- or higher valent polycarboxylic acid (x22) may be charged and allowed to react substantially as monofunctional or bifunctional one, and then polycondensation may be further performed under such conditions that the remaining functional groups are left unreacted. If conditions such as reaction temperature are varied and the (x22) is allowed to react as trifunctional or higher one for crosslinking, a nonlinear polyester resin (B) is formed.
• the reaction ratio between the alcohol component (y) and the carboxylic acid component (x) is preferably set to 2/1 to 1/2, more preferably 1.5/1 to 1/1.3, and particularly preferably 1.3/1 to 1/1.2, expressed by an equivalent ratio [OH]/[COOH] of a hydroxyl group and a carboxylic group.
• the polycondensation of a carboxylic acid component (x) and an alcohol component (y) in obtaining a polyester resin (P) may be carried out using a publicly known esterification reaction.
• the polycondensation may be carried out, for example, by allowing the components to react in an inert gas (nitrogen gas or the like) atmosphere in the presence of a polymerization catalyst, preferably at a reaction temperature of 150 to 280° C., more preferably 180 to 270° C., particularly preferably 200 to 260° C.
• the reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours.
• the polyester synthesized by the above-described method may be subjected to a dehydration reaction at 160 to 180° C. in the presence of a strong acid such as sulfuric acid to form a terminal vinyl group.
• a terminal vinyl group is formed in the linear polyester resin (A)
• a polymerization catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel and aluminum is preferred to use as a polymerization catalyst in terms of reactivity and environmental protection, and it is more preferred to use a titanium-containing catalyst.
• titanium-containing catalyst examples include titanium alkoxides, titanium potassium oxalate, titanium terephthalate, the catalysts disclosed in JP-A-2006-243715[titanium dihydroxybis(triethanolaminate), titanium monohydroxytris(triethanolaminate), titanium diisopropoxybis(triethanolaminate), intramolecular polycondensates thereof, and the like], and the catalysts disclosed in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, and the like).
• antimony-containing catalyst examples include antimony trioxide.
• zirconium-containing catalyst examples include zirconium acetate.
• nickel-containing catalyst examples include nickel acetylacetonate.
• Examples of the aluminum-containing catalyst include aluminum hydroxide and aluminum triisopropoxide.
• the loading amount of the catalyst is determined appropriately so that the rate of reaction is maximum.
• the loading amount is preferably 10 ppm to 1.9%, more preferably 100 ppm to 1.7% relative to all the raw materials. Setting the loading amount to 10 ppm or more is preferred because it affords a high rate of reaction.
• % means % by weight unless otherwise stated.
• the SP value of the linear polyester resin (A) [(cal/cm 3 ) 1/2 ; the same shall apply hereinafter] is preferably 11.0 to 12.8, more preferably 11.2 to 12.6.
• the fixing property (on a higher temperature side) is better, whereas when it is 12.8 or less, the blocking resistance under high-temperature and -humidity conditions is improved.
• the SP value can be adjusted by the composition and the used amount of the carboxylic acid component (x) and the alcohol component (y) as raw materials.
• the SP value in the present invention is calculated by the method proposed by Fedors et al. and disclosed in the following document.
• the acid value (AV) of the linear polyester resin (A) is preferably 0 to 60, more preferably 1 to 55, particularly preferably 2 to 50. If the acid value is 60 or less, the electrification characteristics exhibited in use for a toner do not deteriorate.
• the hydroxyl value (OHV) of the linear polyester resin (A) is preferably 0 to 125, more preferably 1 to 100. When the hydroxyl value is 125 or less, the hot offset resistance and the storage stability achieved in use for a toner are better.
• the acid value and the hydroxyl value in the present invention are measured by the method provided in JIS K0070.
• the peak top molecular weight (hereinafter denoted by Mp) of the linear polyester resin (A) is preferably 2000 to 12000, more preferably 2300 to 11500, particularly preferably 2500 to 11000.
• Mp is 2000 or more, a resin strength required for fixation can be obtained, whereas when it is 12000 or less, the low-temperature fixing property achieved in use for a toner is good.
• the peak top molecular weight (Mp) and the number average molecular weight (Mn) of a polyester resin are measured using gel permeation chromatography (GPC) under the conditions mentioned below.
• Apparatus (example): HLC-8120 manufactured by Tosoh Corporation
• THF tetrahydrofuran
• Standard polystyrene molecular weight 12 points in total, namely, 4480000, 2890000, 1090000, 355000, 190000, 96400, 37900, 18100, 9100, 2800, 1050, and 500.
• a peak top molecular weight Mp
• a solution prepared by dissolving the polyester resin in a THF solvent and separating an insoluble content by filtration with a glass filter was used as a sample solution.
• the softening point [Tm] of the linear polyester resin (A) is preferably 70 to 120° C., more preferably 75 to 115° C., and particularly preferably 80 to 110° C. Within this range, the balance between hot offset resistance and low-temperature fixing property is good.
• Tm is a value measured as follows.
• an elevated flow tester for example, CFT-500D manufactured by Shimadzu Corporation ⁇
• 1 g of a measurement sample is pushed out through a nozzle having a diameter of 1 mm and a length of 1 mm by application of a load of 1.96 MPa by means of a plunger while it is heated at a temperature elevation rate of 6° C./rain, and a graph of the “plunger descending amount (flow value)” and the “temperature” is drawn.
• the temperature corresponding to 1 ⁇ 2 of the maximum value of the descending amount of the plunger is read from the graph, and the value (a temperature at which half of the measurement sample is flowed out) is determined as the softening point [Tm].
• the glass transition temperature [Tg] of the linear polyester resin (A) is preferably 45° C. or higher. When it is 75° C. or lower, the low-temperature fixing property achieved in use for a toner is good.
• Tg is measured by using DSC 20 and SSC/580 manufactured by Seiko Instruments Inc. in accordance with the method (DSC method) provided in ASTM D3418-82.
• the THF-insoluble content in the linear polyester resin (A) is preferably 5% or less in terms of the low-temperature fixing property achieved in use for a toner.
• the THF-insoluble content in the present invention is determined by using the following method.
• the polyester resin (P) contain the nonlinear polyester resin (B) as well as the linear polyester resin (A).
• Examples of the alcohol component (y) that constitutes the nonlinear polyester resin (B) include the aforementioned diols, tri- to octa- or higher hydric polyols, and monools.
• the nonlinear polyester resin (B) is preferably a nonlinear polyester resin [P2(B)] in which the alcohol component (y) [this means, in the present context, an alcohol component that serves as a constitutional unit of the nonlinear polyester resin (B) except alcohol components to be removed from the system during a polycondensation reaction] contains an aliphatic diol (y2) having 2 to 4 carbon atoms in 50 to 95 molar %.
• the content of the (y2) in the [P2(B)] is preferably 60 to 93 molar %.
• Examples of the aliphatic diol (y2) having 2 to 4 carbon atoms include those mentioned above, and two or more thereof may be used in combination.
• y2 Preferred among these (y2) are ethylene glycol and 1,2-propylene glycol, and ethylene glycol is more preferred.
• the carboxylic acid component (x) of the nonlinear polyester resin (B) [hereinafter means both [P1(B)] and [P2(B)]] is preferably composed of a polycarboxylic acid (x2) and, as necessary, a monocarboxylic acid (x1) in terms of electrification characteristics, and is more preferably composed of a monocarboxylic acid (x1) and a polycarboxylic acid (x2).
• Examples of the monocarboxylic acid (x1) include those mentioned above and preferred ones are also the same as those mentioned above.
• the amount of the monocarboxylic acid (x1) in the constitutional units of the nonlinear polyester resin (B) is preferably 30 molar % or less, more preferably 1 to 25 molar %, and particularly preferably 2 to 20 molar % relative to the whole carboxylic acid component (x).
• Examples of the polycarboxylic acid (x2) include those mentioned above.
• dicarboxylic acid (x21) Preferred among the dicarboxylic acid (x21) are alkene dicarboxylic acids having 4 to 20 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof, and terephthalic acid, isophthalic acid, and/or lower alkyl (the number of carbon atoms of alkyl: 1 to 4) esters thereof (x211) are more preferred.
• Preferred among the tri- to hexa- or higher valent polycarboxylic acid (x22) are trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof.
• the content of terephthalic acid, isophthalic acid, and/or lower alkyl (the number of carbon atoms of alkyl: 1 to 4) esters thereof (x211) in the polycarboxylic acid (x2) is preferably 85 to 100 molar %, and more preferably 90 to 100 molar % in terms of storage stability.
• the molar ratio of the terephthalic acid and/or the lower alkyl ester thereof to the isophthalic acid and/or the lower alkyl ester thereof in the (x211) is preferably from 20:80 to 100:0, and more preferably from 25:75 to 80:20 in terms of the mechanical strength of resin.
• the content of the aromatic carboxylic acid in the carboxylic acid component (x) of the nonlinear polyester resin (B) is preferably 80 to 100 molar %, and more preferably 85 to 100 molar % in terms of storage stability and fixing property.
• the content of the aromatic carboxylic acid in the (X) in the whole polyester resin (P) is preferably within the above-mentioned range.
• the nonlinear polyester resin (B) preferably contains at least one of a monool and a monocarboxylic acid (x1) in the carboxylic acid component (x) and/or the alcohol component (y) and more preferably contains the monocarboxylic acid (x1) in the carboxylic acid component (x).
• a monool When a monool is used, it is preferably used in such an amount (calculated value) that 5 molar % or more, more preferably 6 to 85 molar %, particularly preferably 8 to 80 molar %, most preferably 10 to 76 molar %, of the terminal carboxyl groups of the (B) are esterified with the monool in terms of storage stability and production efficiency.
• the monocarboxylic acid (x1) When the monocarboxylic acid (x1) is used, it is preferably used in such an amount (calculated value) that 5 molar % or more, more preferably 6 to 85 molar %, particularly preferably 8 to 80 molar %, most preferably 10 to 76 molar %, of the terminal hydroxyl groups of the (B) are esterified with the (x1) in terms of storage stability and production efficiency.
• reaction conditions of the polycondensation of the carboxylic acid component (x) and the alcohol component (y) in producing the nonlinear polyester resin (B), and the polymerization catalyst to be used are the same as those described for the above-described linear polyester resin (A).
• the reaction ratio between the (y) and the at least part of the (x2) is preferably set to 2/1 to 1/1, more preferably 1.5/1 to 1.01/1, and particularly preferably 1.3/1 to 1.02/1, expressed by an equivalent ratio [OH]/[COOH] of a hydroxyl group to a carboxylic group.
• the reaction ratio between the whole alcohol component (y) and the whole carboxylic acid component (x) to be used for the production of the (B) is preferably set to 2/1 to 1/2, more preferably 1.5/1 to 1/1.3, and particularly preferably 1.3/1 to 1/1.2, expressed by an equivalent ratio [OH]/[COOH] of a hydroxyl group to a carboxylic group.
• the SP value of the nonlinear polyester resin (B) is preferably 11.5 to 13.0, and more preferably 11.7 to 12.8.
• the glass transition temperature [Tg] of the nonlinear polyester resin (B) is preferably 45° C. to 75° C., more preferably 50° C. to 70° C. When the Tg is 75° C. or lower, low-temperature fixing property improves. When the Tg is 45° C. or higher, blocking resistance is good.
• the softening point [Tm] of the (B), which is not particularly limited, is preferably 90° C. to 170° C., more preferably 120° C. to 160° C.
• Tm is 90° C. or higher, hot offset resistance is good, whereas when it is 170° C. or lower, fixing property is good.
• the Mp of the THF-soluble content of the nonlinear polyester resin (B) is preferably 3000 to 30000, more preferably 3200 to 25000, and particularly preferably 3500 to 18000.
• the THF-insoluble content in the nonlinear polyester resin (B) is preferably 3 to 50% in terms of low-temperature fixing property.
• the content is more preferably 5 to 40% and particularly preferably 10 to 35%.
• the gloss of an image is good.
• the acid value (AV) of the nonlinear polyester resin (B) is preferably 0 to 40, more preferably 1 to 30, and the hydroxyl value (OHV) thereof is preferably 0 to 40, more preferably 0 to 32.
• the sum of the acid value and the hydroxyl value of the nonlinear polyester resin (B) is preferably 3 to 40, more preferably 10 to 40, and particularly preferably 15 to 39.
• the storage stability is good, whereas when it is 40 or less, the electrification stability is improved.
• the polyester resin (P) contains the linear polyester resin (A) [preferably [P1(A)]] and the nonlinear polyester resin (B) [preferably [P2(B)]]
• the weight ratio of the (A) to the (B) [(A)/(B); the total is taken as 100] is preferably 10/90 to 90/10, more preferably 20/80 to 80/20 in terms of reconciling low-temperature fixing property, hot offset resistance, and grindability.
• the SP value of the polyester resin (P) [preferably composed of the linear polyester resin (A) and the nonlinear polyester resin (B)] contained in the toner binder of the present invention needs to satisfy the following relationship (1) in terms of fixing property and storage stability and it is preferably 11.6 to 12.9.
• the above-mentioned SP value is a value determined by weighted average from the SP values of the respective resins.
• the HLB value of the polyester resin (P) needs to satisfy the following relationship (2) in terms of fixing property and storage stability and is preferably 5.3 to 7.0.
• the above-mentioned HLB value is a value determined by weighted average from the HLB values of the respective resins.
• the HLB Hydrophile Balance
• the HLB value can be adjusted by the composition, the used amount, and so on of the carboxylic acid component (x) and the alcohol component (y) as raw materials of the polyester resin (P).
• Examples of the method for adjusting the HLB value within the above range include, when the HLB value is reduced,
• Specific examples of (2) include a method of esterifying 5 molar % or more of terminal hydroxyl groups with a monocarboxylic acid, a method of esterifying 5 molar % or more of terminal carboxyl groups with a monool, and a method of modifying 5 molar % or more of terminal hydroxyl groups to vinyl groups, as described above.
• the method (2) is preferred among these, and a method of capping terminal functional groups by esterifying them with a monocarboxylic acid or a monool is more preferred. Particularly preferred is a method of esterifying with a monocarboxylic acid.
• the above method is a useful method because the polyester resin (P2), which contains an aliphatic diol (y2) having 2 to 4 carbon atoms in 50 to 95 molar %, tends to have a higher HLB value.
• the HLB value can be adjusted to within the above-mentioned range by the weight ratio of the (P1) to the (P2).
• the polyester resins (P1) and (P2) to be used for the present invention are allowed to have HLB within the above-mentioned range, and preferably, in terms of improvement in fixing property and storage stability, at least one of them [preferably (P1)] is one in which 5 molar % or more of terminal hydroxyl groups are esterified with a monocarboxylic acid (x1), one in which 5 molar % or more of terminal carboxyl groups are esterified with a monool, or one in which 5 molar % or more of terminal hydroxyl groups are modified to vinyl groups.
• the carboxylic acid component (x) of at least one of the (P1) and the (P2) [preferably (P1)] preferably includes a monocarboxylic acid (x1) and a polycarboxylic acid (x2).
• the polyester resins (P1) and (P2) to be used for the present invention preferably have loss elastic moduli at 120° C. [in the present description also denoted by (P1)[G′′120] and (P2)[G′′120], respectively] (dyn/cm 2 ) satisfying relationship (3), more preferably satisfying relationship (3′).
• the storage elastic modulus of the (P2) at 180° C. [in the present description also denoted by (P2)[G′180]] (dyn/cm 2 ) preferably satisfies relationship (4), more preferably satisfies relationship (4′).
• the loss elastic modulus (G′′) of the polyester resin (P1) or (P2) can be increased by a method of increasing the molecular weight thereof.
• the storage elastic modulus (G′) of the polyester resin (P2) can be increased by increasing the Tm of the (P2), increasing the proportion of a tri- or higher valent constituent to increase the number of crosslinking sites, increasing the molecular weight, and/or increasing the Tg.
• the storage elastic modulus (G′) and the loss elastic modulus (G′′) are measured under the following conditions by using the following viscoelasticity measurement apparatus.
• ARES-24A manufactured by Rheometric Scientific
• the toner binder of the present invention may contain an additional resin other than the polyester resin (P) unless the effect of the present invention is impaired.
• additional resin include vinyl resins [copolymers of styrene and alkyl (meth)acrylate, copolymers of styrene and a diene monomer, and the like], epoxy resins (ring opening polymerization products of bisphenol A diglycidyl ether, and the like), and urethane resins [polyaddition products of the above-mentioned alcohol component (y) and a diisocyanate, and the like].
• the Mp of the additional resin is preferably 300 to 100000.
• the mixability of the (P1) and the (P2) in the polyester resin (P) can be evaluated by observation at a magnification of ⁇ 100 or more (preferably ⁇ 100 to ⁇ 5000) with a phase contrast microscope and a digital microscope (a high resolution optical microscope). Since the toner particle diameter is usually about 5 to about 10 ⁇ m, in the case where the (P1) and the (P2) form a sea-island structure, the mixability is judged good if the dispersion particle diameter of the island phase is 5 ⁇ m or less.
• the dispersion particle diameter is more preferably 4 ⁇ m or less and particularly preferably 0.1 to 3 ⁇ m. If the dispersion particle diameter is 5 ⁇ m or less, the low-temperature fixing property and the hot offset resistance are good.
• the mixability is measured and evaluated by using a phase contrast microscope (an inverted research microscope) IX71 manufactured by OLYMPUS and/or a digital microscope (high resolution zoom lens VH-Z500R/Z 500W) manufactured by KEYENCE Corporation.
• a phase contrast microscope an inverted research microscope
• IX71 manufactured by OLYMPUS
• a digital microscope high resolution zoom lens VH-Z500R/Z 500W manufactured by KEYENCE Corporation.
• the toner binder of the present invention can be processed into a toner of the present invention by adding a coloring agent and, as necessary, one or more additives such as a release agent, a charge controlling agent, a magnetic powder, and a fluidizer.
• any dyes, pigments, and the like used as coloring agents for toners may be used as the colorant.
• Specific examples thereof include carbon black, iron black, Sudan black SM, Fast Yellow G, Benzidine Yellow, Pigment Yellow, Indo Fast Orange, Irgazin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methylviolet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orasol Brown B, and Oil Pink OP, and these may be used singly or two or more of them may be used as a mixture.
• magnetic powders may be added for also serving as a colorant.
• ferromagnetic metals such as iron, cobalt and nickel, or such compounds as magnetite, hematite, and ferrite
• Preferred as the release agent are those having a softening point [Tm] of 50 to 170° C., examples of which include polyolefin waxes, natural waxes, aliphatic alcohols having 30 to 50 carbon atoms, fatty acids having 30 to 50 carbon atoms, and mixtures thereof.
• polyolefin wax examples include (co)polymers of olefins (e.g., ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof) [including those obtained by (co)polymerization and thermo-degradation type polyolefins], oxides with oxygen and/or ozone of (co)polymers of olefins, maleic acid-modified ones of (co)polymers of olefins [e.g., ones modified with maleic acid and derivatives thereof (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, and the like)], copolymers of olefins and unsaturated carboxylic acids [(meth)acrylic acid, itaconic acid, maleic anhydride, and the like] and/or unsaturated carboxylic acid alkyl esters [(me
• Examples of the natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
• Examples of the aliphatic alcohols having 30 to 50 carbon atoms include triacontanol.
• Examples of the fatty acids having 30 to 50 carbon atoms include triacontanoic acid.
• Examples of the charge controlling agent include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium salt group-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, boron complexes of benzilic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.
• Examples of the fluidizer include colloidal silica, alumina powder, titanium oxide powder and calcium carbonate powder.
• the toner binder of the present invention is preferably in a range from 30 to 97%, more preferably from 40 to 95%, and particularly preferably from 45 to 92%;
• the colorant is preferably in a range from 0.05 to 60%, more preferably from 0.1 to 55%, and particularly preferably from 0.5 to 50%;
• the release agent is preferably in a range from 0 to 30%, more preferably from 0.5 to 20%, and particularly preferably from 1 to 10%;
• the charge controlling agent is preferably in a range from 0 to 20%, more preferably from 0.1 to 10%, and particularly preferably from 0.5 to 7.5%;
• the fluidizer is preferably in a range from 0 to 10%, more preferably from 0 to 5%, and particularly preferably from 0.1 to 4%.
• the total content of the additives is preferably 3 to 70%, more preferably 4 to 58%, particularly preferably 5 to 50%.
• the toner may be obtained by any conventionally known method such as a kneading pulverization method, a phase-change emulsion method, and a polymerization method.
• a toner is obtained by using a kneading pulverization method
• components other than a fluidizer that constitute the toner are dry-blended, then melt-kneaded, then coarsely pulverized, finally formed into fine particles by using a jet mill pulverizer or the like, further classified to form fine particles preferably having a particle diameter (D50) within the range of from 5 to 20 ⁇ m, and mixed with a fluidizer, so that the toner can be produced.
• D50 particle diameter
• the average particle diameter (D50) (when particles whose particle diameters are larger than a certain particle diameter account for 50% in number of all particles in the volume particle diameter distribution of a powder, the certain particle diameter is defined as D50) is measured by using a Coulter counter [e.g., commercial name: Multisizer III (manufactured by Coulter)].
• a Coulter counter e.g., commercial name: Multisizer III (manufactured by Coulter)
• a toner is obtained by using a phase-change emulsion method
• components other than a fluidizer that constitute the toner are dissolved or dispersed in an organic solvent, emulsified by, for example, adding water thereto, and separated and then classified, so that the toner can be produced.
• the volume average particle diameter of the toner is preferably 3 to 15 ⁇ m.
• the toner of the present invention using the toner binder of the present invention is, as necessary, mixed with carrier particles such as iron powders, glass beads, nickel powders, ferrite, magnetite, and ferrite with the surface thereof being coated with a resin (an acrylic resin, a silicone resin, and the like), and then used as a developer for an electrostatic latent image.
• carrier particles such as iron powders, glass beads, nickel powders, ferrite, magnetite, and ferrite
• the weight ratio of the toner to the carrier particle is preferably 1/99 to 100/0. It is also possible to form an electric latent image by friction with such a member as a charged blade instead of the carrier particles.
• the toner of the present invention is fabricated into a recording material by being fixed on a supporting material (paper, polyester film, and the like) by a copier, a printer, or the like.
• the method for fixing it onto a supporting material may include known methods such as a heat roll fixing method and a flash fixing method.
• a reaction tank equipped with a stirrer and a nitrogen introduction tube was charged with 500 parts of an adduct of bisphenol A with EO (NEWPOL BPE-20 produced by Sanyo Chemical Industries, Ltd.; the purity of the adduct with 2 EO molecules: about 81%) and then the temperature was raised to 120° C.
• the adduct was dissolved at 120° C., and then the solution was cooled to 100° C.
• a pressurized reaction tank equipped with a stirrer and a nitrogen introduction tube was charged with 277 parts of bisphenol A, 138.5 parts of ion exchange water and 2 parts of triethylamine, followed by flushing with nitrogen twice. Then, the temperature was raised to 130° C. and 123 parts of EO was dropped over 2 hours under a pressure of 0.3 MPa. Then, the mixture was allowed to react for 2 hours and then taken out. Subsequently, water was removed under a reduced pressure of 0.5 to 2.5 kPa at 130° C. for 4 hours, affording a 95% pure adduct of bisphenol A with 2 EO molecules containing an adduct of bisphenol A with one EO molecule in an amount of 0.5%.
• a pressurized reaction tank equipped with a stirrer and a nitrogen introduction tube was charged with 277 parts of bisphenol A, 138.5 parts of ion exchange water and 2 parts of triethylamine, followed by flushing with nitrogen twice. Then, the temperature was raised to 130° C. and 176 parts of EO was dropped over 2 hours under a pressure of 0.3 MPa. Then, the mixture was allowed to react for 2 hours and then taken out. Subsequently, water was removed under a reduced pressure of 0.5 to 2.5 kPa at 130° C.
• an adduct of bisphenol A with 3 EO molecules containing an adduct of bisphenol A with one EO molecule in an amount of 0.1%, an adduct of bisphenol A with 2 EO molecules in an amount of 18%, an adduct of bisphenol A with 3 EO molecules in an amount of 69%, and an adduct of bisphenol A with 4 EO molecules in an amount of 13%.
• reaction tanks used in the following Production Examples were loaded 305 parts (81.2 molar %) of terephthalic acid, 41 parts (14.8 molar %) of benzoic acid, 706 parts (100.0 molar %) of the 95% pure adduct of bisphenol A with 2 EO molecules obtained in Production Example 2, and 2 parts of titanium diisopropoxybistriethanolaminate as a polymerization catalyst, and these were allowed to react with one another at 210° C. under a nitrogen gas flow for 5 hours while generated water being distilled off, and then further allowed to react under a reduced pressure of 0.5 to 2.5 kPa until an acid value of 2 or less was achieved.
• [P1(A)-1] had an Mp of 6200, an Mn of 2300, a Tg of 61° C., a Tm of 100° C., an acid value of 10, a hydroxyl value of 17, a THF-insoluble content of 1%, an SP value of 11.4, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 45 molar %.
• Molar % within parentheses means the molar % of each raw material in a carboxylic acid component or in an alcohol component. The same is applied hereinafter.
• [P1(A)-2] had an Mp of 7800, an Mn of 2700, a Tg of 64° C., a Tm of 105° C., an acid value of 10, a hydroxyl value of 15, a THF-insoluble content of 1%, an SP value of 11.5, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 36 molar %.
• [P1(A)-3] had an Mp of 6400, an Mn of 2400, a Tg of 64° C., a Tm of 105° C., an acid value of 20, a hydroxyl value of 15, a THF-insoluble content of 1%, an SP value of 11.5, an HLB value of 4.5, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 34 molar %.
• [P1(A)-4] had an Mp of 5600, an Mn of 2300, a Tg of 62° C., a Tm of 104° C., an acid value of 10, a hydroxyl value of 13, a THF-insoluble content of 1%, an SP value of 11.7, an HLB value of 4.9, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 52 molar %.
• [P1(A)-5] had an Mp of 6200, an Mn of 2300, a Tg of 59° C., a Tm of 99° C., an acid value of 10, a hydroxyl value of 16, a THF-insoluble content of 1%, an SP value of 11.4, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 45 molar %.
• [P1(A)-6] had an Mp of 7600, an Mn of 2600, a Tg of 62° C., a Tm of 101° C., an acid value of 20, a hydroxyl value of 14, a THF-insoluble content of 1%, an SP value of 11.4, an HLB value of 4.4, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 36 molar %.
• [P1(A)-7] had an Mp of 5000, an Mn of 2200, a Tg of 62° C., a Tm of 106° C., an acid value of 10, a hydroxyl value of 28, a THF-insoluble content of 1%, an SP value of 11.6, an HLB value of 4.9, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 33 molar %.
• [P1(A)-8] had an Mp of 6900, an Mn of 2500, a Tg of 64° C., a Tm of 105° C., an acid value of 10, a hydroxyl value of 23, a THF-insoluble content of 1%, an SP value of 11.3, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 31 molar %.
• [P1(A)-9] had an Mp of 6200, an Mn of 2300, a Tg of 60° C., a Tm of 101° C., an acid value of 20, a hydroxyl value of 30, a THF-insoluble content of 1%, an SP value of 11.4, an HLB value of 4.6, and an esterification ratio of terminal carboxyl groups with a monool of 13 molar %.
• [P1(A)-10] had an Mp of 6300, an Mn of 2400, a Tg of 56° C., a Tm of 96° C., an acid value of 10, a hydroxyl value of 20, a THF-insoluble content of 1%, an SP value of 11.5, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 42 molar %.
• [P1(A)-11] had an Mp of 8000, an Mn of 3100, a Tg of 62° C., a Tm of 108° C., an acid value of 15, a hydroxyl value of 18, a THF-insoluble content of 1%, an SP value of 11.2, an HLB value of 4.4, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 36 molar %.
• [P2(B)-1] had an Mp of 17500, an Mn of 5400, a Tg of 64° C., a Tm of 143° C., an acid value of 1, a hydroxyl value of 14, a THF-insoluble content of 3%, an SP value of 12.3, and an HLB value of 6.8.
• [P2(B)-2] had an Mp of 4800, an Mn of 1700, a Tg of 63° C., a Tm of 155° C., an acid value of 20, a hydroxyl value of 1, a THF-insoluble content of 25%, an SP value of 12.0, an HLB value of 6.2, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 26 molar %.
• [P2(B)-3] had an Mp of 5000, an Mn of 2000, a Tg of 61° C., a Tm of 158° C., an acid value of 24, a hydroxyl value of 2, a THF-insoluble content of 28%, an SP value of 12.1, an HLB value of 6.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 33 molar %.
• [P2(B)-4] had an Mp of 7500, an Mn of 3100, a Tg of 63° C., a Tm of 135° C., an acid value of 1, a hydroxyl value of 31, a THF-insoluble content of 3%, an SP value of 11.7, an HLB value of 5.4, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 48 molar %.
• [P2(B)-5] had an Mp of 5900, an Mn of 3000, a Tg of 66° C., a Tm of 150° C., an acid value of 15, a hydroxyl value of 7, a THF-insoluble content of 21%, an SP value of 12.0, an HLB value of 6.9, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 18 molar %.
• [P2(B)-6] had an Mp of 5200, an Mn of 2500, a Tg of 62° C., a Tm of 155° C., an acid value of 17, a hydroxyl value of 18, a THF-insoluble content of 25%, an SP value of 11.7, an HLB value of 5.7, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 49 molar %.
• RP1-1 had an Mp of 7200, an Mn of 2600, a Tg of 58° C., a Tm of 106° C., an acid value of 20, a hydroxyl value of 14, a THF-insoluble content of 1%, an SP value of 12.1, an HLB value of 6.2, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 41 molar %.
• RP1-2 had an Mp of 7400, an Mn of 3500, a Tg of 59° C., a Tm of 100° C., an acid value of 15, a hydroxyl value of 18, a THF-insoluble content of 1%, an SP value of 10.8, an HLB value of 4.3, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 22 molar %.
• RP2-1 had an Mp of 5000, an Mn of 1900, a Tg of 58° C., a Tm of 155° C., an acid value of 27, a hydroxyl value of 7, a THF-insoluble content of 29%, an SP value of 12.6, an HLB value of 7.4, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 22 molar %.
• RP2-2 had an Mp of 5800, an Mn of 2300, a Tg of 60° C., a Tm of 147° C., an acid value of 12, a hydroxyl value of 35, a THF-insoluble content of 13%, an SP value of 11.2, an HLB value of 4.9, and an esterification ratio of terminal hydroxyl groups with a monocarboxylic acid of 17 molar %.
• the linear polyester resin [P1(A)], the nonlinear polyester resin [P2(B)], the comparative linear polyester resin (RP1), and the comparative nonlinear polyester resin (RP2) obtained in Production Examples 4 to 20 and Comparative Production Examples 1 to 4 were loaded in the proportions given in Table 2 into a plastomill and stirred at 140° C. for 10 minutes, thereby being melted and mixed.
• toner binders (TB-1) to (TB-16) of the present invention made of a polyester resin (P) and comparative toner binders (TB′-1) to (TB′-5) were obtained.
• To 100 parts of each toner binder were added 8 parts of Cyanine Blue KRO (produced by Sanyo Color Works, Ltd.) and 5 parts of carnauba wax. Toner preparation was carried out by the following method.
• the resultant was preliminarily mixed using a Henschel mixer [FM10B manufactured by Nippon Coke & Engineering Co., Ltd.], and then kneaded by a twin screw kneader [PCM-30 manufactured by Ikegai Corporation]. Subsequently, after being finely pulverized using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.], the resulting particles were classified by an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Mfg. Co., Ltd.], so that toner particles having a median diameter (D50) by volume of 8 ⁇ m were obtained.
• MDS-I airflow classifier
• toners (T-1) to (T-16) of the present invention and comparative toners (T′-1) to (T′-5) were obtained.
• Fixation was evaluated in the same manner as in the MFT described above, and the presence or absence of hot offset on a fixed image was visually evaluated.
• the fixing roll temperature at which hot offset occurred was determined as the hot offset occurrence temperature.
• MFT minimum fixing temperature
• HAT hot offset occurrence temperature
• Toners were each placed in a polyethylene bottle, held in a constant temperature water bath at 45° C. for 8 hours, then transferred to a 42-mesh sieve, and then vibrated using a powder tester manufactured by Hosokawa Micron Group at a vibration intensity of 5 for 10 seconds. Subsequently, the amount in % by weight of the toner remaining on the sieve was measured and judged according to the criteria given below, and storage stability was evaluated.
• a 50-ml glass bottle was charged with 0.5 g of a toner binder and 20 g of a ferrite carrier (F-150 produced by Powdertech Co., Ltd.), which were then moisture conditioned at 23° C. and 50% R.H. for 8 hours or more and then frictionally stirred in a Turbula shaker mixer at 50 rpm for 1, 3, 5, 10, 20, and 60 minutes, and the electrification amount was measured at every time.
• a blow off charge amount measuring device [manufactured by KYOCERA Chemical Corporation] was used for the measurement. The electrification amount achieved at a friction time of 10 minutes was taken as a saturated electrification amount.
• the absolute value of the saturated electrification amount is 25 ⁇ C/g or more.
• the absolute value of the saturated electrification amount is 20 ⁇ C/g or more but less than 25 ⁇ C/g.
• the absolute value of the saturated electrification amount is 15 ⁇ C/g or more but less than 20 ⁇ C/g.
• the absolute value of the saturated electrification amount is less than 15 ⁇ C/g.
• ⁇ 0.6 or more but less than 0.7
• ⁇ 0.5 or more but less than 0.6
• ⁇ 0.7 or more but less than 0.8
• ⁇ 0.6 or more but less than 0.7
• the toners (Examples 1 to 16) of the present invention using the toner binders of the present invention were remarkably superior especially in electrification characteristics and blocking resistance to the comparative toners (Comparative Examples 1 to 5) using comparative toner binders.
• the toner of the present invention using the toner binder of the present invention is excellent in fixing temperature range, storage stability, and the like, the toner is useful as a toner to be used for electrophotography, electrostatic recording, electrostatic printing, and the like.

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• 2013
  • 2013-02-25 JP JP2013522416A patent/JP5553941B2/ja active Active
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• 2015
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