WO1999008159A1 - Composition de toner - Google Patents

Composition de toner Download PDF

Info

Publication number
WO1999008159A1
WO1999008159A1 PCT/JP1998/003474 JP9803474W WO9908159A1 WO 1999008159 A1 WO1999008159 A1 WO 1999008159A1 JP 9803474 W JP9803474 W JP 9803474W WO 9908159 A1 WO9908159 A1 WO 9908159A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
units
toner
represented
Prior art date
Application number
PCT/JP1998/003474
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Ito
Original Assignee
Teijin Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Limited filed Critical Teijin Limited
Priority to CA002267551A priority Critical patent/CA2267551A1/fr
Priority to JP51196899A priority patent/JP3862763B2/ja
Priority to AU84637/98A priority patent/AU8463798A/en
Priority to EP98935357A priority patent/EP0930544A4/fr
Publication of WO1999008159A1 publication Critical patent/WO1999008159A1/fr

Links

Classifications

    • 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
    • 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
    • G03G9/08766—Polyamides, e.g. polyesteramides
    • 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
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08768—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only

Definitions

  • the present invention relates to a toner composition useful as a full-color printer for high-speed copying machines. More specifically, the toner composition is excellent in blocking resistance, low-temperature fixing property, and melt fluidity, and is used for developing an electrostatic image or a magnetic latent image in electrophotography or magnetic printing, for example. And a polyesterimide resin that provides the toner composition. Background art
  • an electrostatic image formed on a photoconductive semiconductor or an electrostatic recording medium is developed with a toner charged by friction in advance. And then settled.
  • the latent image on the magnetic drum is developed and fixed by toner containing a magnetic material.
  • the toner image obtained by the development is directly fused on a photoconductive photoreceptor or an electrostatic recording material, or the toner image is transferred onto paper or a film and then fused on a transfer sheet. This is done by letting The fusion of the toner image is usually performed by applying pressure and heating.
  • heating method non-contact heating method using an electric oven or flash light
  • pressure heating method using a pressure roller Is mainly used. The above method is generally called "dry development method”.
  • the toner composition used in the dry development method is prepared by melt-kneading a binder resin as a base, a colorant, a charge control agent, a magnetic powder and other necessary additives, sufficiently dispersing them, and then pulverizing. Manufactured.
  • This resin is the main component of the toner and greatly affects the performance required of the toner. That is, the binder resin for the toner is required to have a good dispersibility of the colorant and the like in the melt-kneading step and good pulverizability in the pulverizing step. Many performances are required, such as good blocking resistance and good electrical properties.
  • epoxy resins epoxy resins, polyester resins, polystyrene resins, acrylic resins, and the like have been generally used.
  • Japanese Unexamined Patent Publication No. Hei 6—1 2 8 3 67 Japanese Patent Publication No. 59-1-19002, Japanese Patent Publication No. 5-85
  • No. 91 describes a polyester resin in which a crosslinked structure is introduced using a monomer having three or more functionalities or a monomer having an unsaturated group as one component in order to improve the resistance to fusing in the fixing step. ing.
  • this branched or cross-linked polyester resin has reduced flowability and is not suitable for high-speed copying or color copying.
  • polyester resin having a linear structure has been proposed as a resin for toner having good melt fluidity.
  • linear polyester resins have a problem that when the melt viscosity is lowered to improve the fluidity, T g is lowered, and the storage stability and anti-blocking property of the toner are lowered.
  • Japanese Unexamined Patent Application Publication Nos. Hei 2-2693964, Hei 4-412161, Hei 5-92778, Hei 5-07705 Polyesters containing 1,2,2-bis (4-hydroxyphenyl) propane (bisphenol A) ethylene oxide or propylene oxide adduct as a diol component are described. This resin has a relatively high Tg and excellent melt flowability.
  • the adduct of bisphenol A with ethylene oxide or propylene oxide usually includes an adduct having a structure in which at least two molecules of ethylene or propylene oxide are added to the OH group of bisphenol A. . Since the aliphatic ether structure contributes to lowering T g, the effect of improving T g cannot be said to be sufficient. In addition, when this polyester is discarded and left outdoors, the alkylene oxide is easily desorbed due to acid treatment conditions such as sewage treatment and acid rain, and has recently become a problem as an “environmental hormone”. Bisphenol A itself may be released to the environment.
  • JP-A-7-16004 and JP-A-8-628-96 disclose flexible diamines. It describes a toner using a polyesterimide resin prepared by melt-polycondensing noalkane ("Jeffamine (JEFFAM IN: manufactured by Texaco Chemical Co., Ltd.)”) with trimellitic anhydride.
  • Japanese Patent Application Laid-Open No. 7-181,738 describes a polyesterimide resin obtained by polycondensing "difamine” and pyromellitic acid anhydride.
  • JP-A-7-160047, JP-A-7-219273, and JP-A-7-333907 also disclose unsaturated compounds together with "diphamine”.
  • Crosslinked polyesterimide resins are disclosed which are prepared by introducing groups and optionally reacting with free radical initiators.
  • polyesterimide resin obtained by polycondensation of difermin J and acid anhydride has extremely high hygroscopicity, when evaluated as a toner, the charge amount at high temperature and high humidity is not sufficiently increased, and there is a problem in fixing property. This is presumed to be due to the inclusion of ether linkages in the imide constituents.
  • the synthesis of diphamine itself goes through many stages, and the cost of the toner as a function of toner is low.
  • the present invention has been problematic in that it can be used as a toner resin that is cost-effective, and an object of the present invention is to provide a novel toner composition.
  • It is yet another object of the present invention to provide a toner composition comprising a polyesterimide having a high glass transition temperature (Tg) and a low melt fusing temperature.
  • Still another object of the present invention is to provide a novel binder resin for toner in which the properties of a polyester resin as a binder resin for toner are improved.
  • Still another object of the present invention is to provide a toner composition useful as a dry toner applicable to a hot roll fixing system, a flash fixing system and the like.
  • a toner composition comprising a color former and at least one polymer selected from the group consisting of A and B,
  • ⁇ 1 is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and a group consisting of an alkylene group having 2 to 20 carbon atoms, an oxyalkylene group, and a polyxylene alkylene group. At least one selected from)
  • a r 2 is a trivalent or tetravalent aromatic hydrocarbon group having 2 6 carbon atoms
  • R 2 is an alkylene group having 2 to 1 2 carbon atoms
  • X is, -CO- or
  • at least one imide unit I selected from the group consisting of units represented by the following formulas: A crosslinked polymer having a number average molecular weight of 2,000 to 10,000, a glass transition temperature of 50 to 90 ° C, a softening temperature of 90 to 160 ° C, and the following formula (A-1)
  • a r 3 is an r-valent aromatic hydrocarbon group having 6 to 12 carbon atoms
  • R 3 is a q-valent aliphatic group having 3 to 9 carbon atoms
  • r and q are 3 or 4
  • a cross-linked polymer mainly composed of at least one type of cross-linking unit C selected from the group consisting of the units represented by the following formulas, and in which the above three units (E, I, C) are bonded by ester bonds.
  • the glass transition temperature is 50 to 90 ° C
  • the softening temperature is 90 to 190 ° C
  • the toner composition of the present invention comprises a color former and a polymer selected from the group consisting of A and B.
  • the polymer A is a polyesterimide mainly composed of an ester unit E represented by the above formula (1) and an imide unit I selected from the group consisting of the units represented by the above formulas (2) and (3). Resin. These units are not linked by an ether bond but are linked by an ester bond.
  • “ 1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • the aromatic hydrocarbon group include a 1,4-phenylene group and a 1,3-phenylene group.
  • Examples include a diene group, a 2-phenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, and a 4,4′-biphenylene group.
  • 1,4-phenylene group and 1,3-phenylene group are preferable.
  • the 1,4-phenylene group accounts for 50 to 80 mol% of the whole, preferably 60 to 80 mol%. 70 mol%.
  • R 1 is selected from the group consisting of alkylene groups having 2 to 20 carbon atoms, xylalkylene groups and polyxylalkylene groups.
  • Examples of such an alkylene group include an ethylene group, a 1,2-propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a neopentylene group (a 2,2-dimethyl-1,3-propylene group), and Examples include groups represented by the following formulas (R l -1) and (R u 2).
  • alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group, a 2-propylene group, and a neopentylene group are more preferable.
  • Examples of such a xyalkylene group include a xydiethylene group and a trioxyethylene group. Among them, a xyxethylene group is preferred.
  • polyxylene alkylene group examples include a polyxylene ethylene group and a polyoxypropylene group.
  • the molecular weight of the polyxylene alkylene group is usually from 500 to 10,000.
  • alkylene groups, substituted xyalkylene groups and polyoxyalkylene groups having 2 to 20 carbon atoms can be used in combination of two or more. In addition, these are usually groups derived from diaryl components.
  • ester unit E represented by the above formula (1) for example, A r 1 is 1, 4 one-phenylene group, 1, 3-phenylene group or a group comprising a combination thereof, and R 1 Ethylene group, 1,2-propylene group, neopentylene group, ethylenediene or An ester unit using a group obtained by combining these groups is preferred.
  • R 1 when R 1 is a xyalkylene group, it is preferably used in combination with an alkylene group.
  • the content of the oxyalkylene group is preferably from 10 to 99 mol%, more preferably from 20 to 85 mol%, and still more preferably from 30 to 80 mol%, based on the alkylene group. Mol%.
  • a derivative derived from a relatively small amount of another dicarboxylic acid component other than the above may be used.
  • examples of such other dicarboxylic acid components include the following.
  • Aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, fumaric acid, adipic acid; cyclohexanedicarboxylic acid, norbornene-2, Alicyclic dicarboxylic acids such as 3-dicarboxylic acid.
  • the proportion of the other dicarboxylic acid component used is preferably 30 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the total acid components constituting the ester unit E. is there.
  • R 1 may be derived from another diol component other than the above, to the extent that physical properties are not impaired.
  • examples of such other diol components include bisphenol A, bisphenol S, bisphenol Z, hydroquinone, 1,4-benzenediol, and 1,3-benzenediol.
  • the amount of such another diol component is preferably 40 mol% or less, more preferably 30 mol% or less, based on the diol component constituting the ester unit E.
  • the ester unit E may contain a small amount of a unit derived from a hydroxycarboxylic acid such as hydroxybenzoic acid and ⁇ -hydroxyxicuronic acid.
  • the proportion of such units is preferably at most 30 mol%, more preferably at most 20 mol%, particularly preferably at most 10 mol%, based on the ester units ⁇ .
  • the formula (2), (3), eight "2 is a trivalent or tetravalent aromatic hydrocarbon group having 2 1 6 carbon atoms,! ⁇ 2 is an alkylene group having 2 to 2 carbon atoms Yes, X is one CO— or one 0—.
  • a r 2 is a trivalent or tetravalent aromatic hydrocarbon group having 6 to 2 carbon atoms.
  • examples of the alkylene group having 2 to 12 carbon atoms include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,4-tetramethylene group, and a hexmethylene group.
  • an alkylene group having 2 to 6 carbon atoms such as an ethylene group and a 1,3-propylene group is preferable, and an ethylene group is particularly preferable.
  • These are usually groups derived from aliphatic amino alcohols and aliphatic amino carboxylic acids.
  • X is one CO— or one tenth.
  • Suitable imide units I represented by the formula (2) for example, A r 2 is 1, 2, 4 benzene combined with other atoms in the ring, R 2 is an alkylene group having 2-6 carbon atoms And an imide unit in which X is — ⁇ — or 1 CO— can be mentioned as a preferable example.
  • a r 2 is 1, 2, 4, 5 in a bond with the benzene ring with another atom
  • R 2 is 2 carbon atoms
  • Preferred is an imide unit which is an alkylene group of 6 and X is -0- or 1CO-.
  • imide unit I examples include a unit represented by the following formula.
  • R 2 1 is an alkylene group having 2 to 6 carbon atoms, an ethylene group is particularly preferred.
  • imide unit I a unit composed of only the unit represented by the above formula (2-1) is particularly preferable.
  • the imide unit I is introduced into the polymer chain having the ester unit E by an ester bond at random or in a specific amount to give an amorphous polymer, and the polyester comprising only the ester unit E While maintaining the excellent melt fluidity possessed by the above, the polyester resin consisting of only the above ester unit alone increases the insufficient Tg and contributes to the storage stability. Further, the present invention can be applied to a positive charging developing method, which has been difficult to apply with a conventional polyester.
  • the polyesterimide resin A preferably has a Tg of 50 to 90 ° C and a softening temperature of 90 to 160 ° C for use as a binder resin for a toner.
  • T g is the temperature at which the inflection point rises when measured by differential scanning calorimetry (DSC) at a heating rate of 20 ° CZ.
  • the softening temperature was measured using a Koka type flow tester, 1 g of the sample was filled under a load of 30 kg, and the temperature was gradually raised from room temperature at a rate of 3 ° CZ. 0% The temperature at the time of melting out from a nozzle with a diameter of 1 mm and a land length of 1 O mm.
  • the Tg of the polyesterimide A When the Tg of the polyesterimide A is lower than 50 ° C, the blocking resistance becomes insufficient, and when the Tg is higher than 9 (TC, the low-temperature fixability becomes insufficient.
  • the Tg is 55 to 85 ° C
  • the softening temperature is lower than 90 ° C, the offset resistance becomes insufficient, and when the softening temperature is higher than 60 ° C, the fluidity of the resin decreases. It is preferable that the temperature be 0 to 150 ° C.
  • the toner composition of the present invention having blocking properties and excellent storage stability as compared with a conventional binder resin for a toner is provided.
  • the molecular weight of the polyesterimide A is preferably adjusted so as to satisfy the thermal characteristics.
  • the number average molecular weight is preferably in the range of 2,000 to 20,000, more preferably 2,000 to 10,000, still more preferably 2,000 to 8,000, and particularly preferably 2,500 to 5,000.
  • the polyester imide resin A has the following formula (A-1)
  • a is the mole% of the ester unit E based on the whole units constituting the non-crosslinked polyesterimide A
  • a 2 is the mole% of the imide unit I.
  • a value of 0.0 smaller than 1 and T g is lower Li a 2, easily occurs blocking upon the Bok na scratch.
  • the softening temperature becomes high, and when evaluated as a toner, the fixing property is deteriorated, and the non-aged fset region becomes a high temperature region.
  • the preferable ratio of a 1 and a 2 satisfies the range of the following formula (A-2), and more preferably the range of the following formula (A-3).
  • the polymer B includes an ester unit E represented by the above formula (1), an imide unit I selected from the group consisting of the units represented by the above formulas (2) and (3), and the above formulas (4) and (4). 5) A crosslinked polyesterimide resin mainly composed of a crosslinking unit C selected from the group consisting of: These units are not linked by an ether bond, but are linked by an ester bond.
  • the crosslinking unit C is selected from the group consisting of the above formulas (4) and (5).
  • " 3 is an r-valent aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • an aromatic hydrocarbon group for example, 1 represented by the above formula (Ar 2 -1) , 2, 4 benzene combined with other atoms in the ring, the formula. (Ar 2 - 2) 1 is expressed by, 2, 4, 5-position with can be mentioned benzene ring bonded with other atoms these Is a group derived from a trivalent or tetravalent aromatic polycarboxylic acid or an anhydride thereof.
  • r 3 or 4.
  • R 3 is a q-valent aliphatic group having 3 to 9 carbon atoms. These are usually groups derived from trihydric or higher polyhydric aliphatic alcohols.
  • the crosslinking unit C is preferably composed of a unit represented by the above formula (5).
  • the above polyesterimide B is represented by the following formula (B-1)
  • b is the mol% of the ester unit E
  • b 2 is the mol% of the imide unit I, based on the whole units constituting the crosslinked polyesterimide B.
  • bzZ ⁇ is smaller than 0.01, the Tg of the polymer becomes low, and blocking tends to occur when the toner is used.
  • it is larger than 0.60, the softening temperature becomes higher, and when evaluated as a toner, the fixability is poor, and the non-offset region becomes a high temperature region.
  • the ratio between bl and b2 preferably satisfies the following expression (B_1-1), and more preferably satisfies the following expression (B1-1-2).
  • polyesterimide B has the following formula (B-2)
  • b is the mole percent of crosslinking units C.
  • bgZfch is smaller than 0.01, the softening temperature of the polymer becomes low, and the storage elastic modulus G 'measured when the temperature is changed from the softening temperature of the resin to 200 ° C using a rheometer 1 is measured.
  • the value in the temperature range of 50 to 200 ° C is small, and when evaluated as a toner, a problem occurs in the offset resistance.
  • the ratio between bl and b2 preferably satisfies the following expression (B-2-1), and more preferably satisfies the following expression (B-2-2).
  • the polyesterimide B preferably has a Tg of 50 to 90 ° C. and a softening temperature of 90 to 190 for use as a binder resin for a toner.
  • T g is the same as in the case of the polyesterimide A.
  • the softening temperature is preferably from 100 to 180 ° C, more preferably from 110 to 160 ° C.
  • the above polymers A and B may contain, if necessary, a small amount of units functioning as heat stabilizers, oxidation stabilizers, light stabilizers, pigment dispersants, dye-fixing agents, flame retardants, etc. It may be contained in the polymer chain in an amount of at most mol%.
  • the agents represented by the following formulas (Other-1), (Other-2), and (Other-3) can be used as an easy fixing agent, a dispersant, and a flame retardant for a colorant, respectively.
  • the desired performance of each agent can be imparted to the polymer by adding them and reacting them at the time of polymer production.
  • the method for producing the polyesterimides A and B in the present invention is not particularly limited, and a conventionally known production method in the art can be employed.
  • an imide unit may be synthesized, and then the dehydration condensation may be performed simultaneously with the esterification method for producing the ester unit E, or the imide precursor may be reacted with the imide precursor. And then subjecting it to dehydration condensation simultaneously with the esterification method for producing the ester unit E, or the raw material for the ester unit and the raw material for the imide unit are placed in the same reaction system. In preparation, the formation of the imide unit I and the formation of the ester unit E may be performed simultaneously. These methods can be used as appropriate.
  • esterification method for producing the ester unit E for example, a direct polymerization method using a dicarboxylic acid component and each glycol component as raw materials, an ester exchange polymerization method using a dicarboxylic acid ester and each daricol component as raw materials, and the like are used. can do.
  • the imide unit I can be produced by reacting an aromatic polycarboxylic acid component with an amino alcohol component or an aminocarboxylic acid.
  • aromatic polycarboxylic acid component include trimellitic anhydride and pyromellitic anhydride. Of these, trimellitic anhydride is preferred in that it gives a more amorphous polyesterimide.
  • Examples of the amino alcohol component include ethanolamine, 2-aminopropanol, and 3-aminopropanol.
  • ethanolamine has good reactivity, gives a more amorphous polyesterimide as described above, and when it remains as an unreacted product, it has a low boiling point, so that it can be easily removed at the latter stage of polymerization. It is good.
  • amino carboxylic acid component examples include 3-amino carboxylic acid, amino carboxylic acid, and the like. Acid, ⁇ -aminocarboxylic acid, and ⁇ -aminocarboxylic acid. Among them, ⁇ -amino carboxylic acid is preferred because it is easy to handle and can be used more inexpensively as a toner resin.
  • ester unit ⁇ can be produced by reacting an aromatic dicarboxylic acid component with a diol component.
  • aromatic dicarboxylic acid components include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and alkyl esters thereof. Of these, terephthalic acid and isophthalic acid are preferred because they can be used as a toner resin at lower cost.
  • diol component examples include, for example, alkylene glycols such as ethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propylene glycol, xyalkylene glycols such as ethylene glycol and triethylene glycol, and polyoxyethylene glycol. , Polyoxypropylene glycol and polytetraethylene glycol. Among these, ethylene glycol and 2-dimethyl-1,3-propylene glycol are preferred in that they do not lower the Tg of the obtained toner, and diethylene glycol is preferable in terms of increasing the melt fluidity of the obtained toner.
  • a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride which is a raw material constituting the imide unit I and an aliphatic component such as ethanolamine are used.
  • Amino alcohol and a diol component such as ethylene glycol, which is one of the raw materials constituting the ester unit E, are first mixed, and reacted at a temperature of 100 ° C or less to form an amide carboxylic acid.
  • the amount of each raw material used is usually from 0.01 to 0.9% by mole of the diol component and from 0.99 to 0.10% by mole of the trivalent or tetravalent component relative to the aromatic dicarboxylic acid component.
  • an equivalent amount of an amino alcohol to the polyvalent aromatic carboxylic acid component is usually from 0.01 to 0.9% by mole of the diol component and from 0.99 to 0.10% by mole of the trivalent or tetravalent component relative to the aromatic dicarboxylic acid component.
  • the imide unit I and the ester unit E can be produced by the same method as described above.
  • the crosslinking unit C is a trivalent or tetravalent aromatic polycarboxylic acid component, a trivalent or tetravalent polycarboxylic acid component. It can be derived from a polyhydric aliphatic alcohol component.
  • the method for producing the polymer B include, for example, a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride, which is a raw material constituting the imide unit I, and an aliphatic amino acid such as ethanolamine.
  • Alcohol and a diol component such as ethylene glycol, which is one of the raw materials constituting the ester unit E, are initially charged and mixed, and reacted at a temperature of 100 ° C or less, and then the remaining raw material components
  • the aromatic dicarboxylic acid component constituting the ester unit E and the aromatic polycarboxylic acid or polyaliphatic alcohol component constituting the cross-linking unit C can be combined with the polyalkylene glycol and Z or polyalkylene as required. There is a method of adding together with the recoiling component and performing polycondensation.
  • a trivalent or tetravalent aromatic polycarboxylic acid component such as trimellitic anhydride
  • trimellitic anhydride it may be mixed at the time of charging.
  • trimellitic anhydride When trimellitic anhydride is used for the imide unit I and the cross-linking unit C, the charging ratio (molar ratio) between trimellitic anhydride and ethanolamine is such that the trimellitic anhydride is excessive.
  • the amount of trimellitic anhydride used is preferably up to 3 times, more preferably 1 to 2 times the amount of ethanolamine.
  • the polyesterimides 8 and B in the present invention can be used by being mixed with another crosslinked or non-crosslinked type binder resin for toner.
  • examples of other toner binder resins to be mixed with the polymer A include the above-mentioned polymer B, bisphenol-based polyester resin, polyester resin having no bisphenol-based component, and styrene-acrylic resin crosslinked resin. Can be mentioned.
  • examples of other binder resins for toner used by mixing with the above polymer B include the above polymer A, bisphenol-based polyester resins, polyester resins other than bisphenol-based resins, and non-crosslinked resins of styrene-acrylic resins. be able to.
  • the physical properties such as Tg and storage elastic modulus G ′ of the above-mentioned polymers A and B can be increased, and the physical properties of the binder as one resin can be further improved. Therefore, when evaluated as a toner, physical properties such as offset resistance can be further improved.
  • the polymers A and B are used in an amount of preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the whole binder resin.
  • the content of the rimer B is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 35% by weight.
  • the resulting mixture (composition) has a number average molecular weight of 3000-50000, a molecular weight distribution of 10-20, a Tg of 60-70C, and a softening temperature of 115-25. It has well-balanced properties as a binder resin for toner at ° C.
  • polyesters A and B in the present invention are appropriately mixed with additives such as a color former, a charge regulator, a wax, and a surface treating agent as a binder resin for a toner to form a toner composition.
  • additives such as a color former, a charge regulator, a wax, and a surface treating agent as a binder resin for a toner to form a toner composition.
  • the amount of the binder resin used in the toner composition is generally 40 to 99% by weight, and preferably 50 to 99% by weight, although it depends on a latent image forming method such as an electrophotographic method and a magnetic method.
  • coloring agent examples include coloring agents such as pigments and dyes.
  • pigments include Ripon Black, such as Colombian's Carbon Black Japan's furnace black trade names Raven5250, Raven5750, Raven1250, Raven1255, and magnetites, such as Colombian Magnetite's trade name MAPI CO BL AC KS And other uniform black pigments.
  • Ripon Black such as Colombian's Carbon Black Japan's furnace black trade names Raven5250, Raven5750, Raven1250, Raven1255, and magnetites, such as Colombian Magnetite's trade name MAPI CO BL AC KS And other uniform black pigments.
  • 1 to 50% by weight, preferably 1 to 30% by weight, of the star is used for the toner.
  • coloring pigments other than black known pigments of cyan, magenta, blue, red, green, brown, yellow or mixtures thereof can be used in the same amount as the above-mentioned black pigment.
  • charge control agent a known charge control agent can be used. Typical examples include azo metal complexes, Nigguchi syn pigments, ammonium salts, aliphatic metal salts, and the like. Generally, the amount is preferably from 15 to 15% by weight based on the toner. Can be used in amounts from 10% to 10% by weight.
  • a known surface treating agent can be used. Typical examples include hydrophobic silica, alumina, titanium oxide, resin ultrafine particles, and the like. Generally, 0.1 to 10% by weight, preferably 0.1 to 7% by weight based on the toner. Can be used.
  • waxes can be used as the wax.
  • polypropylene polyethylene (molecular weight 1 000-10000), higher fatty acid salts, etc.
  • an amount of 0.5 to 10% by weight, preferably 55% by weight, based on the toner can be used.
  • the above-mentioned toner composition after containing the above-mentioned additives, is subjected to known pulverization, pulverization and classification steps, and then adjusted as toner particles having an average particle diameter of 7 to 20 m as measured by a Coulter Counter. You can do it.
  • the toner composition of the present invention may contain a small amount of a heat stabilizer, an oxidation stabilizer, a light stabilizer, a pigment dispersant, a dye easy fixing agent, a flame retardant, and a dye, if necessary, for example, 20% by weight of the whole. It may be included below.
  • the toner composition of the present invention is particularly excellent in melt fluidity, fixability, offset resistance, and blocking resistance by using the above-mentioned polyester imide resin having both high Tg and low softening temperature as a binder resin. Is good. Therefore, this toner composition is extremely useful for electrophotographic printers, magnetic printers and the like.
  • the polyesterimide of the present invention has a feature that it can be used as a binder resin for a positively charged toner.
  • conventional polyester resins could only use the negative charging method due to the characteristics of the polymer. Since such a polyesterimide has a specific imide unit, it is easy to impart a brush charging property as compared with a conventional polyester resin, and can be used as a positive charging type toner.
  • the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.
  • “parts” means “parts by weight”.
  • the reduced viscosity (7? SpZC) of the polymer was measured using a phenol Z1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 64) at a polymer concentration of 1.2 g / d I and a temperature of 35 ° C. did.
  • the Tg of the polymer was determined as follows using a differential scanning calorimeter “DSC220” manufactured by Seiko Instruments Inc. First, when heated to 200 ° C in 20 ° C for 20 minutes, rapidly cooled with dry ice, and then heated again at a rate of 2 (measured around the baseline of the chart and Tg when measured at TC / min). The temperature at the intersection of the tangents to the endothermic curve was defined as Tg.
  • the softening temperature is 1 mm * X 10 mm using “K0KA FLOW TESTER” manufactured by Shimadzu Corporation.
  • the measurement was performed under the conditions of a nozzle with a load of 30 kgf. This refers to the temperature at which 1/2 of 1 g of the sample melted out at an isothermal rate of 3 ° CZ for the sample.
  • the average molecular weight (Mw and Mn) was adjusted by dissolving 2 Omg of each sample with 1 OmI of THF, and using GPC column ⁇ Shodex KF-80MJ in series of 4 The molecular weight of each sample was measured using a connected Shodex “GPC system-11j” and converted to standard polystyrene.
  • polyesterimide resin was subjected to the following toner tests (1) to (3) and evaluated as a resin for a toner binder.
  • the print density of the printed matter obtained by the simple fixing test is measured. Next, apply a sticky cellophane tape to the same place, rub it back and forth with a 1 kg roller 20 times, measure the print density after peeling off the tape, and compare the print density ratio before and after peeling the tape. The fixing rate (%) was used. The print density was measured using a reflection densitometer.
  • the powder sample was dropped from the container into a 20-mesh sieve.
  • a predetermined amount of aminoethanol, trimellitic anhydride, and propylene glycol shown in the table are placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel is replaced with nitrogen gas at room temperature. Then, the reaction vessel was heated to 50 ° C. under normal pressure. After reacting for 30 minutes, Predetermined amounts of dimethyl terephthalate and diethylene glycol shown in Table 1 were added, and 4 parts of tetrabutyl titanate were further added, and the reaction vessel was heated to 200 ° C under normal pressure. After maintaining the reaction temperature at 200 ° C. for 3 hours, the temperature was raised to 220 ° C., and the reaction was further performed for 1.5 hours.
  • Table 1 shows the results of the number average molecular weight, Tg, and softening temperature of the polymer thus obtained.
  • the polyesterimide resin of the present invention has a low Tg and a low softening temperature due to the introduction of an aromatic imide group, and is excellent in offset properties, fixing properties and blocking resistance. Has excellent characteristics.
  • Table 2 shows the results of the number average molecular weight, Tg, and softening temperature of the polymer thus obtained.
  • reaction was carried out at 240 ° C for 1 hour in a nitrogen gas stream under normal pressure, for 15 minutes under a weak vacuum of about 2 OmmHg, and further for 120 minutes under a high vacuum of 1 mmHg or less.
  • a non-crosslinked polyester resin was obtained.
  • Table 2 shows the number average molecular weight, Tg, and softening temperature of the polymer thus obtained. Show.
  • Table 2 shows the results of the number average molecular weight, Tg, and softening temperature of the blend polymer obtained in this manner.
  • polyester (imide) resins of Examples 4 and 5 and Comparative Example 2 5 parts by weight of carbon black and 1 part of a charge control agent were added and melt-kneaded by a twin-screw extruder.
  • the obtained pellet was pulverized by a jet mill and classified by a classifier to obtain a toner having a particle diameter of 10 to 15 m.
  • Table 2 shows the results of evaluation of this toner by the above method.
  • the polyesterimide resin for a toner according to the present invention may have an aromatic imide group introduced therein. It has a low softening temperature despite its high Tg, and has excellent offset properties, fixing properties, and blocking resistance, and has well-balanced properties as a binder resin for toner.
  • a predetermined amount of aminoethanol, trimellitic anhydride, and propylene glycol shown in Table 3 were put into a reaction vessel having a distilling system through a stirrer and a rectification column, and the reaction vessel was filled with nitrogen gas at room temperature. The reaction vessel was replaced, and the reaction vessel was heated to 50 ° C under normal pressure. After reacting for 30 minutes, predetermined amounts of dimethyl terephthalate, diethylene glycol and polyhydric diol shown in Table 3 were added, 60 parts of tetrabutyl titanate was further added, and the reaction vessel was heated to 200 ° C under normal pressure. After maintaining the reaction temperature at 200 ° C for 8 hours, the temperature was raised to 230 ° C and the reaction was further performed for 2 hours.
  • the obtained polymer was pale yellow and transparent, was insoluble in THF, and the molecular weight could not be measured.
  • Tables 3 and 4 show the results of the number average molecular weight, Tg, and softening temperature of this polymer.
  • reaction was carried out at 240 ° C for 1 hour in a nitrogen stream under normal pressure, for 15 minutes under a weak vacuum of about 20 mmHg, and further for 120 minutes under a high vacuum of 1 mmHg or less.
  • the obtained polymer was colorless and transparent, had a number average molecular weight of 250, Tg of 61 ° C, and a softening temperature of 11 ° C.
  • polyesterimide resins obtained in Examples 6 to 8 and the polyester resin obtained in Reference Example 1 were subjected to a biaxial extruder (PCM 3 manufactured by Ikekai Iron Works Co., Ltd.) in a specific composition ratio shown in Table 5 below. Using 0), the composition was melt-extruded and mixed at a cylinder temperature of 230 ° C. to produce a composition.
  • PCM 3 manufactured by Ikekai Iron Works Co., Ltd.
  • the obtained blend polymer (composition) was yellow and transparent.
  • Number average molecular weight, glass Table 5 shows the transition temperature and softening temperature.
  • Table 5 shows the results of the evaluation of this toner by the above method.
  • a predetermined amount of aminoethanol, polycarboxylic anhydride, and ethylene glycol shown in Table 6 were placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel was filled with nitrogen gas at room temperature. The reaction vessel was replaced, and the reaction vessel was heated to 50 ° C under normal pressure. After reacting for 30 minutes, add the prescribed amounts of dimethyl terephthalate, diethylene glycol or neopentyl glycol, and glycerin shown in Table 6 and then add 60 parts of tetrabutyltyl titanate. Heated to C. After maintaining the reaction temperature at 200 ° C.
  • Table 6 shows the results of the number average molecular weight, Tg, and softening temperature of this polymer.
  • a predetermined amount of aminoethanol, trimellitic anhydride, and ethylene glycol shown in Table 7 were placed in a reaction vessel having a distilling system via a stirrer and a rectification column, and the reaction vessel was replaced with nitrogen gas at room temperature. Then, the reaction vessel was heated to 50 ° C. under normal pressure. After reacting for 30 minutes, add the specified amount of dimethyl terephthalate, dimethyl isophthalate, diethylene dalichol or neopentyl dalicol shown in Table 7, and further add 4 parts of tetrabutyl titanate. Was heated to 2000C. After maintaining the reaction temperature at 200 ° C. for 3 hours, the temperature was raised to 220 ° C., and the reaction was further performed for 1.5 hours.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

Cette invention concerne une composition de toner qui comprend un agent formateur de couleur ainsi qu'un polymère au moins choisi dans le groupe comprenant A et B. A représente un polyesterimide non réticulé comprenant des unités ester E et des unités imide I spécifiques, tandis que B représente un polyesterimide réticulé comprenant les unités E et I ainsi que des unités de réticulation C. Cette composition possède une excellente fluidité à l'état fondu ainsi qu'une excellente capacité de fixation. Elle possède en outre d'excellentes propriétés anti-décalage et de résistance au blocage, et peut être électrifiée positivement.
PCT/JP1998/003474 1997-08-05 1998-08-04 Composition de toner WO1999008159A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002267551A CA2267551A1 (fr) 1997-08-05 1998-08-04 Composition de toner
JP51196899A JP3862763B2 (ja) 1997-08-05 1998-08-04 トナー組成物
AU84637/98A AU8463798A (en) 1997-08-05 1998-08-04 Toner composition
EP98935357A EP0930544A4 (fr) 1997-08-05 1998-08-04 Composition de toner

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP9/210574 1997-08-05
JP21057497 1997-08-05
JP9/210572 1997-08-05
JP21057297 1997-08-05
JP9/318290 1997-11-19
JP31829097 1997-11-19

Publications (1)

Publication Number Publication Date
WO1999008159A1 true WO1999008159A1 (fr) 1999-02-18

Family

ID=27329140

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/003474 WO1999008159A1 (fr) 1997-08-05 1998-08-04 Composition de toner

Country Status (6)

Country Link
EP (1) EP0930544A4 (fr)
JP (1) JP3862763B2 (fr)
KR (1) KR20000068695A (fr)
AU (1) AU8463798A (fr)
CA (1) CA2267551A1 (fr)
WO (1) WO1999008159A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142432A3 (fr) * 2008-05-19 2010-02-11 Samsung Fine Chemicals Co., Ltd. Encre en poudre contenant une résine de liaison présentant les propriété d'une cire et procédé permettant de préparer l'encre en poudre

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07134446A (ja) * 1993-11-11 1995-05-23 Sanyo Chem Ind Ltd トナーバインダー
JPH07219273A (ja) * 1994-02-02 1995-08-18 Xerox Corp トナー、及び架橋ポリエステルイミドの調製方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59120632A (ja) * 1982-12-27 1984-07-12 Toshiba Corp ポリエステルイミド誘導体の製造方法
JPS59204051A (ja) * 1983-05-07 1984-11-19 Canon Inc 電子写真現像粉
DE3537230A1 (de) * 1985-10-19 1987-04-23 Huels Chemische Werke Ag Polyesterimide und verfahren zu ihrer herstellung
US5348831A (en) * 1993-10-28 1994-09-20 Xerox Corporation Polyester-imide toner and developer compositions
US5427882A (en) * 1994-07-29 1995-06-27 Xerox Corporation Low melt polyester imide toner compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07134446A (ja) * 1993-11-11 1995-05-23 Sanyo Chem Ind Ltd トナーバインダー
JPH07219273A (ja) * 1994-02-02 1995-08-18 Xerox Corp トナー、及び架橋ポリエステルイミドの調製方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0930544A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142432A3 (fr) * 2008-05-19 2010-02-11 Samsung Fine Chemicals Co., Ltd. Encre en poudre contenant une résine de liaison présentant les propriété d'une cire et procédé permettant de préparer l'encre en poudre

Also Published As

Publication number Publication date
EP0930544A4 (fr) 2000-08-16
AU8463798A (en) 1999-03-01
KR20000068695A (ko) 2000-11-25
EP0930544A1 (fr) 1999-07-21
JP3862763B2 (ja) 2006-12-27
CA2267551A1 (fr) 1999-02-18

Similar Documents

Publication Publication Date Title
JP4990048B2 (ja) トナー用バインダー樹脂組成物およびトナー
JP3971228B2 (ja) 電子写真用トナー
EP2212369B1 (fr) Résine de polyester et toner comprenant celle-ci
JP4394014B2 (ja) 接触定着電子写真用非晶質ポリエステル
JP2002284866A (ja) 結晶性ポリエステル
WO2003001302A1 (fr) Resine polyester pour toner, son procede de production et toner la contenant
JP2003043741A (ja) ポリエステル樹脂及びこれを含むトナー
JPH1160703A (ja) トナー用ポリエステル樹脂、その製造方法およびそれを用いたトナー
WO2004057419A2 (fr) Composition de resine polyester pour poudre imprimante et poudre imprimante
US5270436A (en) Polyester for electrophotography
JP2004309517A (ja) トナーの製造方法
JP3984335B2 (ja) トナー用ポリエステル樹脂、その製造方法およびそれを用いたトナー
WO1999008159A1 (fr) Composition de toner
JP3738012B2 (ja) トナー用樹脂組成物およびトナー
KR20070012889A (ko) 토너용 폴리에스테르 수지, 및 이를 사용하여 제조되는토너
JP3426007B2 (ja) トナー用ポリエステル樹脂
JP3521505B2 (ja) トナー用ポリエステル樹脂およびトナー
JPS60214368A (ja) 電子写真現像剤組成物
JP3828872B2 (ja) トナー用線状ポリエステル樹脂、トナー、及びトナー用線状ポリエステル樹脂の製造方法
JP3714731B2 (ja) トナー用ポリエステル樹脂
JPS6067958A (ja) 電子写真用トナ−
US8133650B2 (en) Polyester resin and toner including the same
JP2907493B2 (ja) トナー用ポリエステル樹脂
KR101471419B1 (ko) 폴리에스테르 수지 및 이를 포함하는 토너
JP3975105B2 (ja) ポリエステル系トナー組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

WWE Wipo information: entry into national phase

Ref document number: 84637/98

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2267551

Country of ref document: CA

Ref country code: CA

Ref document number: 2267551

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 09269657

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1019997002880

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1998935357

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1998935357

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998935357

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997002880

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1019997002880

Country of ref document: KR