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WO2013038955A1 - Composition de résine et son procédé de fabrication, et toner l'utilisant - Google Patents

Composition de résine et son procédé de fabrication, et toner l'utilisant Download PDF

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Publication number
WO2013038955A1
WO2013038955A1 PCT/JP2012/072470 JP2012072470W WO2013038955A1 WO 2013038955 A1 WO2013038955 A1 WO 2013038955A1 JP 2012072470 W JP2012072470 W JP 2012072470W WO 2013038955 A1 WO2013038955 A1 WO 2013038955A1
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Prior art keywords
resin
group
acid
formula
resin composition
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Japanese (ja)
Inventor
細川　隆史
清隆 深川
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature

Definitions

  • the present invention relates to a resin composition, a method for producing the same, and a toner using the same.
  • the electrophotographic method applied to copiers and the like is now widespread and can be used to instantly copy not only black and white images but also many good color images.
  • This electrophotography is typically performed by the following apparatus and process (see FIG. 1).
  • the surface of the photosensitive member (latent image holding member) 1 using a photoconductive substance is charged by the charging unit 8 and exposed to light L to form a latent image electrically.
  • a toner image is formed by applying toner from the drum 3 stored in the toner supply chamber 2 to the latent image formed here.
  • the toner 5 is charged to a charge opposite to that of the photoreceptor.
  • the toner image is transferred onto the surface of a transfer medium such as paper 4 via an intermediate transfer body (not shown) as necessary.
  • a desired image can be obtained by fixing the transfer image 51 by heating, pressurization, solvent vapor or the like.
  • the toner remaining on the surface of the photoreceptor is cleaned by the cleaner 7 as necessary, and is used again for developing the toner image. Further, the photoconductor is neutralized by a static eliminator 9 to prepare for the next copy.
  • Patent Document 1 discloses an attempt to reduce a difference in glossiness and unevenness in a chemical toner.
  • the toner contains a resin mainly composed of a high molecular compound, and the influence on the environment related to its production cannot be ignored. Since there is no external shape like a molded body, it tends to be overlooked, but there is a great potential for improving environmental compatibility as a resin product that is consumed in large quantities.
  • polymers derived from fossil fuels are usually used, and from the viewpoint of recent environmental problems, it is desired to replace them with those derived from natural resources with low equivalent carbon dioxide emission.
  • Patent Documents 2 to 5 There are examples of using rosin components or rosin esters, which are natural materials, as toner materials. According to this, substitution to the natural material can be realized. However, with the above toner, sufficient performance cannot be obtained, and a resin with improved characteristics has been desired.
  • the present applicant first paid attention to an abietan-based compound derived from a natural resource, and succeeded in producing a polymer incorporated in the main chain. And the physical property of the polymer was confirmed, and it discovered that high heat resistance and moisture-and-water resistance could be expressed (Unexamined-Japanese-Patent No. 2011-26569, Unexamined-Japanese-Patent No. 2011-74249).
  • the above polymer was made into a copolymer having a specific structure, and by blending with a specific resin, it succeeded in expressing properties suitable as a toner material.
  • the present invention contributes to the preservation of the global environment by using a plant-derived compound, is excellent in production suitability when used as a toner, and can exhibit sufficient performance as a toner, and its production It is an object to provide a method and a toner using the method.
  • a resin composition comprising resin B.
  • G 1 represents an alkane linking group or alkene linking group having 4 or more carbon atoms, and X, Y, and Z each independently represents a divalent linking group.
  • R 1 represents a substituent.
  • X 2 represents a divalent linking group or a single bond.
  • G represents a divalent linking group.
  • N1 represents an integer of 0 to 4.
  • nb represents an integer of 0 to 3.
  • L 12 in the formula (A1) is — (C ⁇ O) — * or — (C ⁇ O) O— *
  • (* Represents the side of the bond in the above formula. In the formula, L 13 represents a divalent linking group.)
  • R 3 represents a substituent.
  • N 3 represents an integer of 0 to 4.
  • nc represents an integer of 0 to 3. * is incorporated into the main chain.
  • the ring Ar represents an aryl linking group.
  • G 4 and G 5 each represent a divalent linking group.
  • R 4 represents a substituent.
  • N4 represents an integer of 0 to 4.
  • nc represents an integer of 0 to 3. * is incorporated into the main chain.
  • the ring Ar represents an aryl linking group.
  • the weight average molecular weight of the resin A is 7,000 or more and 25,000 or less, and the weight average molecular weight of the resin B is more than 25,000 and not more than 70,000, any one of [1] to [11]
  • a toner comprising the resin composition according to any one of [1] to [14].
  • a method for producing a resin composition wherein the resin component of the resin composition according to any one of [1] to [15] is mixed and aggregated in an emulsified and dispersed state.
  • the resin composition of the present invention has environmental compatibility by utilizing a compound of plant origin. Further, since it has good compatibility with the crystalline resin, it is suitable as a toner material, and sufficient performance can be exhibited when the toner is used, such as fixability. Moreover, according to the manufacturing method of this invention, said resin composition can be manufactured suitably. Furthermore, since the toner of the present invention uses the resin having the above-mentioned excellent properties, it exhibits excellent characteristics as a toner, and is a next-generation toner capable of sufficiently replacing the resin of artificial origin while being compatible with the environment. As an advantage. The above and other features and advantages of the present invention will become more apparent from the following description and accompanying drawings.
  • 1 is a side view of an apparatus schematically shown for explaining a copying machine based on electrophotography and a copying process thereof.
  • 2 is a DSC chart of polymer P-1 prepared in Example.
  • the resin of the present invention consists of a specific polymer using a plant-derived compound, and has good properties as a resin for toner while being derived from a plant.
  • the reason for this is estimated as follows. That is, the specific polymer has a skeleton derived from dehydroabietic acid as its basic skeleton. A structure in which the tricyclic portion including the benzene ring is two-dimensionally connected as a parent is stable and may contribute to stabilization of the toner characteristics.
  • Tg which is too high as a toner is improved.
  • Resin A (Repeating unit containing a skeleton derived from dehydroabietic acid)
  • resin A also referred to as the specific polymer A
  • dehydroabietic acid represented by the following formula (AA) or a derivative thereof is used as a raw material monomer.
  • AA a homopolymer obtained by polymerizing this may be a copolymer obtained by polymerizing the raw material monomer and another monomer. That is, the specific polymer has a repeating unit containing a skeleton derived from dehydroabietic acid in its molecular structure.
  • the “skeleton derived from dehydroabietic acid” only needs to have a structure derived from the above-mentioned dehydroabietic acid, in other words, dehydroabietic acid within a range where a desired effect is achieved. Any structural skeleton that can be derivatized from the above is acceptable. However, the tricyclic mother nucleus structure of dehydroabietic acid is maintained (the number of atoms constituting the ring may not be maintained), and one of them must include a benzene ring. To do. Preferable examples include the following.
  • the skeleton derived from dehydroabietic acid may further have a substituent.
  • substituents include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, a carbonyl group, a nitro group, and an amino group.
  • (AA-1), (AA-3), and (AA-10) are preferable, and (AA-1) is most preferable.
  • Specified polymer A preferably includes a structure represented by the following formula (U) as a skeleton derived from the dehydroabietic acid when generalized.
  • R A and R B represent an alkyl group or alkenyl group having 1 to 6 carbon atoms.
  • n represents 0-3.
  • m represents 0-5.
  • Ring Cy represents a saturated or unsaturated 6-membered or 7-membered ring which may contain a hetero atom.
  • * and ** represent a bond incorporated into the main chain. * May be a bond extending from RA .
  • R B is preferably a methyl group.
  • R A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an i-propyl group.
  • Cy is preferably a cyclohexane ring or a cyclohexene ring, and more preferably a cyclohexane ring.
  • n and m are preferably 1.
  • the above formula (U) is preferably the following formula (U1).
  • R A , R B , m, and n are as defined in the above formula (U).
  • R C has the same meaning as R B.
  • p is an integer of 0 to 2, and is preferably 0.
  • Dehydroabietic acid is one of the components constituting rosin contained in pine resin of plant origin. That is, since a material of natural origin can be used as its substrate, it is offset in the amount of carbon dioxide emission, and the equivalent emission amount can be greatly reduced as compared with a plastic material of fossil fuel origin. It is an environmentally-friendly material derived from biomass resources that is desired as a next-generation material.
  • the skeleton derived from the above dehydroabietic acid and the skeleton represented by the formulas U, U1 or U2 may be collectively referred to as a dehydroabietane main skeleton, and this may be abbreviated as “DHA main skeleton”. There is.
  • examples of the skeleton structure important in a preferred embodiment of the present invention include those represented by the following formulas U3 and U4.
  • the thing of the following formula U3 is called a dehydroabietane skeleton (DA skeleton), and the thing of the formula U4 is called a dehydroabietic acid skeleton (DAA skeleton).
  • the specific polymer is preferably selected from a polymer containing a repeating unit represented by the following formula A01 or A02, more preferably selected from a polymer containing a repeating unit represented by the formula A11 or A12. It is particularly preferable that the polymer is selected from polymers containing a repeating unit represented by A1 or A2.
  • R A , R B , R C , m, n, p, and Cy are synonymous with the above formulas (U) and (U1).
  • L 11 , L 12 , L 21 , L 22 , and L 23 represent a divalent linking group. * Represents a bond.
  • L 11 When it is a repeating unit derived from polycarboxylic acid L 11 : * -CO-L 13 -** or * -L 13 -CO-** (L 13 represents a linking group. See below for details. )
  • L 12 , L 21 , L 22 Carbonyl group
  • L 23 Oxygen atom, sulfur atom, carbonyl group, sulfonyl group, alkylene group, alkenylene group, arylene group, or single bond
  • L 12 , L 21 , L 22 When a repeating unit derived from a polyol L 11 : * -L 1A -O-** (L 1A represents a linking group. See below for details.)
  • L 12 , L 21 , L 22 * — CH 2 —O — ** L 23 is as defined above.
  • the linking group L 11 is preferably bonded to the carbon atom shown at the 2-position in the formula.
  • the linking group L 23 is bonded to the carbon atom represented by the 2-position and 2'-position in the formula.
  • the repeating unit having a skeleton derived from dehydroabietic acid preferably has a molar ratio of 5 to 40%, more preferably 10 to 30%, in relation to the copolymerization component described later. preferable.
  • the copolymerization ratio is equal to or higher than the lower limit, the amount of the natural product-derived component in the resin can be increased, and when the copolymerization ratio is equal to or lower than the upper limit, the resin can be provided with appropriate flexibility. This is preferable.
  • the specific polymer A in the present invention has a structural unit represented by the following formula (I) as a copolymerization component.
  • G 1 represents an alkane linking group or alkene linking group having a total carbon number of 4 or more.
  • G 1 may be linear or branched, and one or more hydrogen atoms may be substituted with a specific substituent or may be unsubstituted. Examples of the substituent when substituted include the substituent T described later, and among them, an alkyl group and an alkenyl group are preferable.
  • One or more carbon atoms may be substituted with a heteroatom, and examples of the heteroatom when substituted include an oxygen atom, a nitrogen atom, and a sulfur atom, and an oxygen atom is preferable (typically (In other words, a part of the alkylene chain is linked by replacing an ether bond).
  • the total number of carbons means that when the alkylene group or alkenylene group has a substituent, the number of carbon atoms is included.
  • G 1 is preferably an alkane linking group or alkene linking group having 4 to 18 carbon atoms in total, and more preferably 6 to 14 carbon atoms. These linking groups may be substituted or unsubstituted, and a part thereof may be substituted with a hetero atom as described above.
  • — (CH 2 ) 4 —, — (CH 2 ) 5 —, — (CH 2 ) 8 —, — (CH 2 ) 10 —, — (CHRa) CH 2 —, —CH 2 —Rb—CH 2 —, — (CH 2 CH 2 O) 2 —CH 2 CH 2 —, and — (CH 2 CH 2 O) 3 —CH 2 CH 2 — are more preferred.
  • Ra is preferably an alkyl group having 6 to 16 carbon atoms, and more preferably C 12 H 23 or C 8 H 15 .
  • Rb is preferably a cycloalkylene group having 4 to 12 carbon atoms, and more preferably a cyclohexanediyl group.
  • ⁇ X, Y, Z X, Y, and Z each independently represent a divalent linking group.
  • a divalent linking group selected from the group consisting of these, and —O—, — (C ⁇ O) O—, — (C ⁇ O) NH—, or — (C ⁇ O) — is more preferable.
  • R is a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), or an alkenyl group (preferably having 1 to 5 carbon atoms).
  • the bonding mode is not particularly limited.
  • the weight average molecular weight of the specific polymer is not limited, but is preferably 10,000 or more and 25,000 or less, more preferably 7000 or more and 25,000 or less. When the weight average molecular weight is within this range, melt viscosity, glass transition temperature, flexibility and the like particularly suitable as a resin for toner are realized and improved.
  • the weight average molecular weight in this invention is the value obtained by the molecular weight measurement (polystyrene conversion) by gel permeation chromatography (GPC). Unless otherwise specified, in this specification, tetrahydrofuran is used as a carrier, and molecular weight is indicated by a value using TSK-gel Super AWM-H (trade name) manufactured by Tosoh Corporation as a column.
  • the glass transition temperature (Tg) is not limited, but is preferably 30 ° C. or higher, more preferably 40 to 80 ° C., and further preferably 45 to 65 ° C. When the glass transition temperature is within this range, it is possible to achieve both the fixability particularly when used as a toner and the thermal stability over time.
  • the glass transition temperature depends on the method and conditions employed in the examples described below unless otherwise specified.
  • the specific polymer includes derivatives obtained by further subjecting a polymer having a repeating unit containing a DA main skeleton to chemical treatment.
  • the specific polymer is a copolymer having a polyester structure in which the DA main skeleton is derived from the dicarboxylic acid (specific polymer (1)), or the DA main skeleton is derived from the diol. It is preferable that it is a copolymer (specific polymer (2)) which has a polyester structure.
  • the alkylene group and alkenylene group may be linear or branched, or cyclic.
  • L 13 is an alkylene group having 2 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, an oxygen atom, a carbonyl group, a single bond, or a single bond thereof, from the viewpoint of heat resistance
  • a combination is preferred. More preferably, it is a chain alkylene group or carbonylalkylene group having 2 to 4 carbon atoms, a cyclic alkylene group or carbonylalkylene group having 5 to 6 carbon atoms, or a chain alkenylene group or carbonylalkenylene group having 2 to 4 carbon atoms.
  • substituent T examples include the following.
  • An alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohex
  • linking group represented by L 13 include the following, but the present invention is not construed as being limited thereto.
  • the bond * is the side bonded to the hydrophenanthrene ring, and the bond ** means the opposite side.
  • L 13 in the formula (A1) is a single bond, (L1-ex-4), (L1-ex-10) or (L1-ex) from the viewpoint of various physical properties when used as a resin and ease of synthesis. ⁇ 12) is preferable, and a single bond is more preferable. More preferably, L 11 is * —CO — **, * —CO — **, * —CO—Rd—COO — ** (Rd is an alkylene group having 1 to 6 carbon atoms).
  • the linking group L 11 may be bonded to any of the carbon atoms at the 1-position, 2-position, and 4-position in the formula, but is bonded to the carbon atom shown at the 2-position or 4-position. It is preferable that it is a thing couple
  • ⁇ L 12 L 12 is preferably a carbonyl group.
  • Another preferred embodiment of the specific polymer (1) is a repeating unit having a dimer structure in which two dehydroabietane main skeletons are bonded directly or via a linking group as a part of the main chain. It is included.
  • the repeating unit containing this dimer structure is represented by the above formula (A2), for example.
  • Repeating unit represented by Formula A2 ⁇ ⁇ L 21, L 22 L 21 and L 22 in Formula A2 are preferably a carbonyl group or a carbonyloxy group. This means that the specific polymer of this embodiment has a repeating unit containing a DAA skeleton, like L 12 above.
  • L 23 is preferably an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an alkylene group, an alkenylene group, an arylene group, or a single bond.
  • the alkylene group and alkenylene group may be linear or branched, or cyclic.
  • the linking group represented by L 23 is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an alkylene group having 2 to 10 carbon atoms, a carbon number from the viewpoint of various physical properties when used as a resin and ease of synthesis.
  • It is preferably composed of at least one selected from the group consisting of an alkenylene group having 2 to 10 carbon atoms and an arylene group having 6 to 18 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and 2 to A chain alkylene group having 5 to 6 carbon atoms, a cyclic alkylene group having 5 to 6 carbon atoms, a chain alkenylene group having 2 to 4 carbon atoms, a cyclic alkenylene group having 5 to 6 carbon atoms, and an arylene having 6 to 8 carbon atoms More preferably, it is a divalent linking group composed of at least one selected from the group consisting of groups, or a single bond.
  • the alkylene group, alkenylene group and arylene group constituting the linking group represented by L 23 may have a substituent, if possible.
  • substituent in the alkylene group, alkenylene group, and arylene group include the substituent T.
  • Specific examples of the linking group represented by L 23, may be mentioned the following linking groups, the present invention is not limited thereto.
  • L 23 is (L2-ex-2), (L2-ex-5), (L2-ex-9) or (L2-ex) from the viewpoints of various physical properties when used as a resin and ease of synthesis. ⁇ 11) is preferred, and (L2-ex-2) is more preferred.
  • the linking group L 11 may be bonded to any of the carbon atoms in the 1-position, 2-position, 4-position, 1′-position, 2′-position and 4′-position in the formula, but the 2-position It is preferable that it is bonded to the carbon atom shown at the 4-position, 2′-position, and 4′-position (however, it is a combination connecting two hydrophenanthrene rings). More preferably, it is bonded to the indicated carbon atom. This bonding position is the same for the specific polymer (2) described later.
  • the copolymerization ratio of the repeating unit composed of the DHA main skeleton is in the range described above.
  • Dehydroabietic acid used in the production of the specific polymer (1) of the present embodiment can be obtained from rosin, for example. Constituents contained in rosin vary depending on the method of collection and the production area of pine, but in general, abietic acid (1), neoabietic acid (2), parastrinic acid (3), levopimaric acid (4), It is a mixture of diterpene resin acids such as dehydroabietic acid (5), pimaric acid (6) and isopimaric acid (7).
  • each compound represented by (1) to (4) is disproportionated by heat treatment in the presence of a certain kind of metal catalyst, and dehydroabietic acid (5)
  • dihydroabietic acid (8) having the structure described below That is, the dehydroabietic acid (5) necessary for producing the specific polymer (1) of the present invention can be obtained relatively easily by subjecting rosin, which is a mixture of various resin acids, to an appropriate chemical treatment. And can be manufactured industrially at low cost.
  • Dihydroabietic acid (8) and dehydroabietic acid (5) can be easily separated by a known method.
  • the step of synthesizing the specific polymer (1) having the repeating unit represented by the above formula (A1) or (A2) and the repeating unit represented by the formula (I) is represented by the formula (I).
  • a polycondensation of a polyol compound forming a repeating unit and a dicarboxylic acid compound forming a repeating unit represented by the above formula (A1) or (A2) or a dicarboxylic acid halide derivative or a diester derivative thereof by a known method. can be synthesized.
  • Specific methods for synthesizing polymers include, for example, the methods described in New Polymer Experimental Science 3, Polymer Synthesis / Reaction (2), pp. 78-95, Kyoritsu Publishing (1996) (for example, transesterification method).
  • Direct esterification method melt polymerization method such as acid halide method, low-frequency solution polymerization method, high-temperature solution polycondensation method, interfacial polycondensation method, etc.).
  • the method and the direct ester method are preferably used.
  • the transesterification method is a method of synthesizing a specific polymer (1) by subjecting a polyol compound and a polycarboxylic acid ester derivative to a dealcoholization polycondensation by heating in a molten state or a solution state, if necessary, in the presence of a catalyst. .
  • the direct esterification method is a method of synthesizing a specific polymer (1) by dehydrating polycondensation of a polyol compound and a polycarboxylic acid compound in the presence of a catalyst in a molten state or a solution state under heating.
  • the acid halide method is a method of synthesizing a specific polymer (1) by heating a polyol compound and a polycarboxylic acid halide derivative in a molten state or in a solution state, if necessary, in the presence of a catalyst and dehydrohalogenating polycondensation. It is.
  • a specific compound (1) is prepared by dissolving a polyol compound in water, the polycarboxylic acid compound or a derivative thereof in an organic solvent, and polycondensing at a water / organic solvent interface using a phase transfer catalyst. Is a method of synthesizing.
  • a dimer of dehydroabietic acid (DAA) of the formula (A2) can be synthesized by the method described in JP2011-26569A. Specifically, when connecting the L 23 represents a single bond, can be advanced a catalytic amount of N, the reaction by the addition of N- dimethylformamide with oxalyl chloride. When L 23 is a methylene group, a method of replacing the oxalyl chloride with dichloromethane is exemplified. Alternatively, the reaction may be allowed to proceed by mixing DAA with formalin and adding a catalytic amount of trifluoroacetic acid.
  • dicarboxylic acid compound (formula I-1) or diol compound (formula I-2) is used as the monomer constituting the structural unit represented by formula (I) separately from the DHA main skeleton. It is preferable.
  • diol dicarboxylic acid is demonstrated here as an example, as above-mentioned, this may be a polyol polycarboxylic acid.
  • G 1A has the same meaning as G 1 in formula (I).
  • G 1A means a linking group forming a part of G 1.
  • —CO—G 1A —CO— corresponds to G 1. Also good.
  • G 2 to G 5 , R 3 , R 4 , n3 and n4 are as defined in the following formulas (II) to (III).
  • Each of the above general formula monomers may be used alone or in combination of two or more.
  • the use ratio of each monomer is preferably in the range of the copolymerization ratio described above for the specific polymer.
  • the specific polymer (1) of the present embodiment may be a copolymer with other polycarboxylic acid compounds.
  • polycarboxylic acid compounds usually used for constituting polyesters can be used without particular limitation.
  • synthetic polymer V Asakura Shoten
  • the polycarboxylic acid compounds described in 63-91 and the like can be used.
  • polycarboxylic acid compounds examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dicyclohexanedicarboxylic acid, and adipic acid.
  • polyol compounds include polyols having a ring structure and polyols having no ring structure.
  • the ring structure contained in the polyol compound may be an aliphatic ring or an aromatic ring, and may be a hydrocarbon ring or a heterocyclic ring. Further, the aliphatic ring may contain an unsaturated bond.
  • the number of rings contained in the polyol compound is not particularly limited, but can be, for example, 1 to 5, and is preferably 1 to 3 from the viewpoint of various physical properties and availability when used as a resin. More preferably, it is ⁇ 2.
  • the structure may be a structure in which two or more monocycles are linked by a covalent bond or a linking group, or may be a condensed ring structure.
  • repeating unit derived from the polyol compound having a ring structure examples include, for example, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxypropoxy).
  • examples thereof include a repeating unit derived from benzene, 4-hydroxyethylphenol, and the like, and a repeating unit derived from a diol compound represented by the following formula (B1).
  • a polyol compound usually used for constituting the specific polymer (1) can be used without particular limitation, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3.
  • the DHA main skeleton is derived from a diol compound, and the linking groups are as follows.
  • ⁇ L 11 L 11 is a single bond, * -L 1A -O-**. * Represents a bond on the hydrophenanthrene ring side, and ** represents the opposite bond.
  • the single bond or divalent linking group represented by L 1A is not particularly limited, and examples of the linking group include — (C n H 2n ) —, —CO (C n H 2n ) —, (here N is an integer of 1 to 12, preferably 1 to 8, which may be linear, branched or cyclic, and may further have a substituent, and may be one of the carbon atoms constituting the molecular chain. One or more may be replaced with an oxygen atom).
  • the atom bonded to L 1A is an oxygen atom, it is preferably — (CH 2 ) 4 —, — (CH 2 ) 5 —, — (CH 2 ) 6 — or the like.
  • the atom bonded to L 1A is a carbonyl group, preferably — (CH 2 ) 3 —, — (CH 2 ) 4 —, — (CH 2 ) 5 —, —CO (CH 2 ) 2 —, —CO ( CH 2 ) 3 —, —CO (CH 2 ) 4 — and the like.
  • ⁇ L 23 L 23 has the same meaning as described above, and the preferred range is also the same.
  • the dicarboxylic acid form of dehydroabietic acid can be synthesized in the same manner as the specific polymer (1).
  • the reaction from a dicarboxy compound obtained by introducing a carboxy group into abietic acid to a dialkoxy compound may be performed by an ordinary reduction reaction.
  • the reduction reaction can be rapidly advanced by reducing with aluminum hydride.
  • the reaction for obtaining a polyester from a dialkoxy compound by a reaction with a polycarboxylic acid chloride compound may be performed by a conventional method.
  • the process of reacting the dialkoxy compound with terephthalic acid dichloride is the same as described in the specific polymer (1).
  • a dicarboxylic acid may be reacted to cause an esterification reaction to proceed or a transesterification reaction may be performed, and such a reaction is also the same as described in the specific polymer (1).
  • dicarboxylic acid compounds or diol compounds combined with the diol compound having the DA main skeleton are the same as those described in the specific polymer (1).
  • the compounds exemplified in formula (I-1) can be preferably used. You may use the monomer which makes other copolymerization components. Examples thereof include other dicarboxylic acid or diol compounds described in the polymer (1).
  • JP, 2011-026569, A can be referred to for the details of the production method and the compound of the specific polymer (1).
  • JP, 2011-074249, A can be referred to for the details of the production method and the compound of the specific polymer (2).
  • a to u each mean a molar ratio of each monomer unit, and also serves as the name of the unit.
  • the resin composition of the present invention contains, as the resin B, a polymer containing a structural unit represented by the following formula (IIa) (also referred to as a specific polymer B).
  • Ar Ring Ar represents an aromatic ring, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. The same applies to the following formulas (IIb), (II), (III), and (IIb ′).
  • ⁇ R 1 R 1 represents a substituent.
  • the substituent include the substituent T.
  • a monovalent organic group is preferable, and an alkyl group, an alkoxy group, and an aryl group are more preferable.
  • the preferable carbon number etc. are further synonymous with the substituent T.
  • ⁇ X 2 X 2 each independently represents a divalent linking group or a single bond.
  • Preferable ones are independently —O—, —S—, —NR—, — (C ⁇ O) —, —O (C ⁇ O) —, — (C ⁇ O) O—, — (C ⁇ O) represents a divalent linking group selected from the group consisting of NR—, an alkylene group having 1 to 8 carbon atoms, an alkynylene group having 2 to 8 carbon atoms, and combinations thereof.
  • Preferred is —O—, — (C ⁇ O) O—, — (C ⁇ O) NH—, or — (C ⁇ O) —.
  • R is a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), or an alkenyl group (preferably having 1 to 5 carbon atoms).
  • nb n1 represents an integer of 0 to 4.
  • nb represents an integer of 0 to 3.
  • G represents a divalent linking group, and is preferably a linking group having the same meaning as X 2 or a linking group having an aromatic ring (a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or the like).
  • the linking group having an aromatic ring is preferably the following formula (IIb).
  • R 2 , Z 2 and n2 in the formula have the same meanings as R 1 , X 2 and n1, respectively.
  • ** represents a bond on the * bond side in formula (IIa). * Is the opposite bond.
  • na represents an integer of 0 to 3.
  • Ar is as defined above.
  • Y 2 represents a divalent linking group composed of at least one selected from the group consisting of an oxygen atom, a carbonyl group, a sulfonyl group, a sulfur atom, an imino group, and an alkylene group, or a single bond. When a plurality of Y 2 are present, each Y 2 may be the same or different.
  • the alkylene group constituting the divalent linking group in Y 2 may be a linear or branched chain alkylene group or a cyclic alkylene group.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Note that the carbon number of the alkylene group here does not include the carbon number of the substituent (side chain).
  • the alkylene group may have a substituent such as a linear or cyclic alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or the like.
  • the number of substituents in the alkylene group may be two or more.
  • the alkylene group has two or more substituents, the two or more substituents may be the same or different, and are connected to each other to form a ring. May be.
  • Y 2 may form a ring by sharing a carbon atom with the aromatic ring Ar in the formulas (IIa) and (IIb).
  • the ring preferably has 5 to 12 carbon atoms including a shared carbon atom.
  • the structural unit represented by the formula (IIa) is preferably a structural unit represented by the following formula (II).
  • G 2 and G 3 each represent a divalent linking group or a single bond, preferably an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, a linking group containing a ring structure, or a single bond.
  • G 2 and G 3 may be linear, branched or include a ring structure.
  • a linking group containing a ring structure there is preferably a linking group containing an aromatic ring, and more preferably a linking group represented by the following formula (IIb ′).
  • R 2 and n2 in the formula have the same meanings as R 1 and n1, respectively.
  • Y 2 has the same meaning as in formula (IIb). ** represents a bond on the oxygen atom side. * Represents the opposite bond.
  • na represents an integer of 0 to 3.
  • Ar represents an aromatic ring.
  • R 3 R 3 represents a substituent, and a preferred range thereof is the same as R 1 .
  • n3 represents an integer of 0 to 4.
  • nc represents an integer of 0 to 3.
  • the structural unit represented by the formula (IIa) is a structural unit represented by the following formula (III).
  • G 4 and G 5 each represent a divalent linking group. Its preferred range is the same as defined in the G 2 or G 3.
  • R 4 represents a substituent, and its preferred range is the same as R 1 .
  • n4 represents an integer of 0 to 4.
  • nc represents an integer of 0 to 3. * Represents a bond incorporated in the main chain.
  • formula (IIa) is preferably the following formula (IIa ′).
  • R 11 and R 12 R 11 and R 12 each independently represents a hydrogen atom or a substituent.
  • substituents include the substituent T.
  • a monovalent organic group is preferable, and a methyl group, an ethyl group, and a phenyl group are more preferable.
  • X 2 , Y 2 and Z 2 each represent a divalent linking group or a single bond, and a preferred range thereof is as defined in the above formulas (IIa) and (IIb). * Is a bond.
  • N11 and n12 represent an integer of 0 to 4, preferably 0 to 2.
  • nd represents an integer of 0 to 3, and preferably 1 or 2.
  • the copolymerization ratio of the repeating unit represented by the formula (IIa) is preferably 5 to 50%, more preferably 10 to 50% in terms of molar ratio.
  • Tg and flexibility particularly suitable for use as a resin for toner can be expressed, which is preferable.
  • the specific polymer may have other copolymer components, and the copolymer ratio is preferably suppressed to 95% or less in terms of molar ratio. Although there is no particular lower limit, it is practical to set the lower limit to about 50% when other copolymerization components are present.
  • the molecular weight of the specific polymer B is not particularly limited, but is preferably 9,000 or more and 200,000 or less in terms of weight average molecular weight, and more preferably 10,000 or more and 100,000 or less.
  • the resin B is obtained, for example, by condensation polymerization of an alcohol component containing a divalent alcohol compound containing at least an alkylene oxide adduct of a bisphenol compound represented by the following formula (IIb) and a carboxylic acid component. It is preferable.
  • R 15 and R 16 are both alkylene groups having 2 to 4 carbon atoms.
  • Each of R 13 and R 14 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group.
  • nb and nc are both integers of 0 or more, and the sum thereof is 1 to 16.
  • nb and nc are positive integers, and the sum thereof is more preferably 2 to 16. More preferably, each of nb and nc is 1 to 4.
  • Examples of the alkylene oxide adduct of the bisphenol compound represented by the above formula contained in the divalent alcohol compound used as the alcohol component in the condensation polymerization of the polyester resin B include, for example, bisphenol A, bisphenol F, ethylene oxide, And diols obtained by polymerization with a cyclic ether such as propylene oxide.
  • an alcohol other than the bisphenol compound represented by the above formula may be contained as long as the intended effect is not impaired.
  • the content of the alkylene oxide adduct of the compound is preferably 80 mol% or more in the divalent alcohol compound.
  • Divalent carboxylic acid and polyvalent carboxylic acid more than trivalence can be suitably selected according to the objective.
  • the divalent carboxylic acid component includes benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof.
  • Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc.
  • saturated dibasic acid anhydride examples include, for example, trimet acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid.
  • an aromatic polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or the like is contained from the viewpoint of heat-resistant storage stability and mechanical strength of the resin.
  • the content of the aromatic polycarboxylic acid compound is preferably 40 mol% to 95 mol%, more preferably 50 mol% to 90 mol%, still more preferably 60 mol% to 80 mol% in the carboxylic acid component.
  • the catalyst and conditions for the polymerization reaction may be determined according to conventional methods. JP, 2011-2802, 2009-3136, etc. can be referred to for detailed synthesis procedures and addition amounts.
  • the resin composition of the present invention contains the resin A and the resin B.
  • the blending ratio of the two is not particularly limited, but it is preferable to blend 5 to 300 parts by weight of resin B, and more preferably 15 to 200 parts by weight with respect to 100 parts by weight of resin A.
  • the specific polymer (resin A) derived from dehydroabietic acid, the resin B, and the crystalline resin used in combination to expand the fixing temperature range are three. Excellent compatibility.
  • the compatibility between the three means that the resin A and the resin B of the present embodiment exhibit good compatibility, and for example, the compatibility between the resin A (or the resin B) and the crystalline resin is not good.
  • the compatibility between the resin A / resin B mixture and the crystalline resin is good.
  • the resin composition of the present embodiment for a toner, an image having excellent transparency and glossiness can be obtained. Therefore, particularly when the toner is combined with a color material for color, a high-quality color image is obtained, which is preferable.
  • the resin composition of the present invention is preferably used as a toner material.
  • the type of toner is not particularly limited, and may be a toner by a pulverization method or a chemical toner prepared by emulsion aggregation or the like.
  • the resin composition of the present invention is more preferably used for a chemical toner in that the characteristics of the resin composition are more remarkable.
  • an embodiment as a chemical toner will be mainly described.
  • the aromatic dicarboxylic acid used as the acid component in (a) is phthalic acid, terephthalic acid, isophthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, and acid anhydrides thereof. And derivatives such as lower alkyl esters and the like. Among these, it is particularly preferable to use at least one selected from the group consisting of terephthalic acid, isophthalic acid, and derivatives thereof.
  • the lower alkyl esters of terephthalic acid and isophthalic acid may be used.
  • lower alkyl esters of terephthalic acid and isophthalic acid include, for example, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, Although there are dibutyl terephthalate, dibutyl isophthalate, and the like, dimethyl terephthalate and dimethyl isophthalate are preferable in terms of cost and handling (handling).
  • These dicarboxylic acids or lower alkyl esters thereof may be used alone or in combination of two or more. Since terephthalic acid and isophthalic acid have an aromatic ring, Tm and Tg of the resin can be adjusted to an appropriate range as a resin for toner, and offset resistance and blocking resistance are improved. Appropriate strength can be given.
  • Disproportionated rosin is a rosin containing abietic acid as a main component that is heated at a high temperature in the presence of a noble metal catalyst or halogen catalyst to eliminate unstable conjugated double bonds in the molecule.
  • abietic acid As a mixture of dehydroabietic acid and dihydroabietic acid.
  • the component of the disproportionated rosin those containing 45% by weight or more of dehydroabietic acid are preferable, and those containing 50% by weight or more are particularly preferable.
  • the trihydric or higher polyhydric alcohol used as the alcohol component may be at least one selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin and pentaerythritol. These trihydric or higher polyhydric alcohols react with the aromatic dicarboxylic acid used as the acid component of (a) to form a polyol structure having an appropriate branch. By imparting an appropriate branched structure to the polyester resin, it is possible to maintain low temperature fixability without excessively increasing the Tm of the resin, obtain a wide molecular weight distribution toward the high molecular weight side, and improve offset resistance.
  • the molar ratio (3) / (1) is lower than 1.05, the molecular weight distribution on the high molecular weight side becomes too wide and Tm becomes high, so that the low-temperature fixability decreases, or the high molecular weight side. It becomes impossible to control the spread of the molecular weight distribution, and gelation is likely to occur.
  • it becomes a polyester resin with few branches As a result, Tm and Tg fall and the tendency for blocking resistance to fall comes out.
  • An aliphatic polycarboxylic acid can be further used as the acid component of (a).
  • the aliphatic polycarboxylic acid those generally applied to this type of polymer can be used.
  • the amount of the resin C is not particularly limited, but is preferably 0 to 100 parts by mass, and more preferably 0 to 50 parts by mass with respect to 100 parts by mass of the resin A.
  • the aqueous resin dispersion of the present embodiment includes at least one specific polymer derived from the dehydroabietic acid, which is dispersed in an aqueous medium. Composed.
  • the polymer derived from dehydroabietic acid can constitute an aqueous dispersion excellent in self-dispersibility and dispersion stability.
  • the acid value of the specific polymer is 5 mgKOH / g or more and 25 mgKOH / g or less.
  • the acid value is equal to or higher than the above lower limit value, a sufficient surface charge can be imparted to the resin particles when an aqueous resin dispersion is formed. Therefore, the dispersion stability is good, aggregation can be suppressed, and a resin having a desired particle size. It is preferable because particles can be obtained. Further, when the acid value is not more than the above upper limit, hydrophilicity is appropriate, generation of coarse particles can be suppressed, and a good particle size distribution can be obtained. Further, the acid value is more preferably 10 mgKOH / g or more and 15 mgKOH / g or less from the viewpoint of the dispersion stability.
  • self-dispersibility refers to, for example, a functional group (particularly an acidic group or a salt thereof) possessed by the polymer itself when it is in a dispersed state (particularly, a dispersed state by a phase inversion emulsification method) in the absence of a surfactant. It means that it can be dispersed in an aqueous medium, and it means that a resin dispersion containing no free emulsifier can be constituted.
  • the dispersed state refers to both an emulsified state (emulsion) in which the polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which the polymer is dispersed in a solid state in an aqueous medium.
  • the polymer A is preferably a water-insoluble polymer.
  • the water-insoluble polymer is a polymer having a dissolution amount of 10 g or less when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., and the dissolution amount is preferably 5 g. Hereinafter, it is more preferably 1 g or less.
  • the dissolution amount is the dissolution amount when neutralized with sodium hydroxide or acetic acid according to the kind of the salt-forming group of the water-insoluble polymer.
  • phase inversion emulsification method for example, a polymer is dissolved or dispersed in a solvent (for example, a hydrophilic organic solvent) and then poured into water as it is without adding a surfactant.
  • a solvent for example, a hydrophilic organic solvent
  • the dispersion state of the polymer particles refers to a solution obtained by dissolving 30 g of a polymer in 70 g of an organic solvent (for example, methyl ethyl ketone), a neutralizing agent capable of neutralizing 100% of the salt-forming group of the polymer (a salt-forming group is an anion).
  • an organic solvent for example, methyl ethyl ketone
  • a neutralizing agent capable of neutralizing 100% of the salt-forming group of the polymer (a salt-forming group is an anion).
  • Sodium hydroxide, acetic acid if cationic) and 200 g of water are mixed and stirred (apparatus: stirring apparatus with stirring blades, rotation speed 200 rpm, 30 minutes, 25 ° C.)
  • Even after removing the organic solvent it means a state in which the dispersed state can be visually confirmed to exist stably at 25 ° C. for at least one week.
  • the toner binder of the present embodiment contains at least one polymer derived from dehydroabietic acid, and includes other components (for example, a resin) as necessary.
  • the toner binder can be applied to either a dry kneading and pulverizing method or a wet method of granulating toner particles in a liquid.
  • the specific polymer derived from dehydroabietic acid is excellent in self-dispersibility and dispersion stability, and therefore can be suitably used in a wet method for granulating toner with the polymer in a dispersed state.
  • the toner binder of the present embodiment can contain at least one other resin as its component.
  • the other resin include crystalline resins, and examples thereof include polyester resins other than the polymer derived from dehydroabietic acid (hereinafter also referred to as “other polyester resins”).
  • other polyester resins include polyester resins other than the polymer derived from dehydroabietic acid (hereinafter also referred to as “other polyester resins”).
  • the composition means that two or more components exist substantially uniformly in a specific composition.
  • substantially uniform means that each component may be unevenly distributed within the range where the effects of the invention are exerted.
  • the composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring.
  • Other polyester resins are obtained, for example, mainly by polycondensation of polyvalent carboxylic acids and polyhydric alcohols.
  • polyvalent carboxylic acid examples include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and the like; maleic anhydride, fumaric acid, succinic acid, Examples thereof include aliphatic carboxylic acids such as alkenyl succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and one or more of these polyvalent carboxylic acids can be used. Among these polyvalent carboxylic acids, it is preferable to use an aromatic carboxylic acid.
  • the polyester resin preferably has a cross-linked structure or a branched structure.
  • a trivalent or higher carboxylic acid trimellitic acid or tricarboxylic acid
  • a dicarboxylic acid It is preferable to use the acid anhydride or the like together.
  • polyhydric alcohol examples include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol And alicyclic diols such as A; aromatic diols such as ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A.
  • aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin
  • cyclohexanediol, cyclohexanedimethanol hydrogenated bisphenol And alicyclic diols
  • aromatic diols such
  • the polyester resin has a cross-linked structure or a branched structure. Therefore, as the polyhydric alcohol, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane) is used together with the diol. , Pentaerythritol) may be used in combination.
  • a trihydric or higher polyhydric alcohol glycolin, trimethylolpropane
  • Pentaerythritol may be used in combination.
  • the glass transition temperature (hereinafter sometimes abbreviated as “Tg”) of other polyester resins is preferably 40 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° C. or lower.
  • Tg of the polyester resin is 80 ° C. or lower, low-temperature fixability is obtained, and when the Tg is 40 ° C. or higher, sufficient heat storage properties and storability of fixed images are obtained.
  • the molecular weight (weight average molecular weight) of other polyester resins is preferably 5,000 or more and 40,000 or less from the viewpoints of resin manufacturability, fine dispersion during toner production, and compatible toner during melting.
  • polyester resins contain at least 1 type of crystalline polyester resin.
  • the polyester resin contains a crystalline polyester resin, the low-temperature fixability of the toner becomes better. Further, since the heating temperature in the fixing process is low, deterioration of the fixing device is suppressed.
  • the polyester resin contains a crystalline polyester resin and an amorphous polyester resin, the crystalline polyester resin is compatible with the amorphous polyester resin at the time of melting, and the viscosity of the toner is significantly reduced. A toner with excellent properties can be obtained.
  • the crystalline polyester resins aliphatic crystalline polyester resins are particularly preferable because many of them have a preferable melting point as compared with aromatic crystalline resins.
  • the content of the crystalline polyester resin in the polyester resin is preferably 2% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 14% by mass or less.
  • the content of the crystalline polyester resin is 2% by mass or more, the non-crystalline polyester resin can be sufficiently reduced in viscosity at the time of melting, and an improvement in low-temperature fixability is easily obtained.
  • the content of the crystalline polyester resin is 20% by mass or less, the deterioration of the charging property of the toner due to the presence of the crystalline polyester resin can be suppressed, so the image strength after fixing on the recording medium Is easy to obtain.
  • the melting point of the crystalline polyester resin is preferably in the range of 50 ° C. or higher and 100 ° C. or lower, preferably in the range of 55 ° C. or higher and 95 ° C. or lower, and more preferably in the range of 60 ° C. or higher and 90 ° C. or lower. . If the melting point of the crystalline polyester resin is 50 ° C. or higher, the storage stability of the toner and the storage stability of the toner image after fixing are good, and if it is 100 ° C. or lower, the low-temperature fixability is easily improved.
  • the crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component.
  • the “acid-derived component” is a polyester resin, and before the polyester resin is synthesized.
  • the component part which was an acid component is pointed out, and the “alcohol-derived component” refers to the component part which was an alcohol component before the synthesis of the polyester resin.
  • Acid-derived constituent component examples include various dicarboxylic acids, but the acid-derived constituent component in the crystalline polyester resin according to the embodiment is a linear aliphatic dicarboxylic acid. Is desirable. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecane Dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof And acid anhydrides, but are not limited thereto
  • acid-derived component other components such as a dicarboxylic acid-derived component having a double bond and a dicarboxylic acid-derived component having a sulfonic acid group may be contained.
  • Constituent mol% means that the acid-derived constituent component in the entire acid-derived constituent component in the polyester resin or the alcohol constituent component in the entire alcohol-derived constituent component is 1 unit (mol). ) Indicates the percentage.
  • Alcohol-derived constituent component The alcohol to be an alcohol constituent component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6.
  • 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability and cost.
  • the molecular weight (weight average molecular weight) of the crystalline polyester resin is preferably 8,000 or more and 40,000 or less, from the viewpoint of resin manufacturability, fine dispersion during toner production, and compatible toner during melting. More preferably, it is 000 or more and 30,000 or less. If it is 8,000 or more, the resistance reduction of the crystalline polyester resin can be suppressed, so that the charging property can be prevented from decreasing. If it is 40,000 or less, the cost of resin synthesis is suppressed, and the low-temperature fixability is not adversely affected in order to prevent a decrease in sharp melt properties.
  • the toner binder of the present embodiment may contain other resins than the polyester resin.
  • resins such as polyethylene and polypropylene
  • styrene resins such as polystyrene and ⁇ -polymethylstyrene
  • (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile
  • polyamide resins polycarbonate resins, polyether resins and These copolymer resins are exemplified.
  • the content of the polymer A derived from dehydroabietic acid in the toner binder of the present embodiment is preferably 10 to 95% by mass, and more preferably 20 to 80% by mass in the total solid content. preferable.
  • the crystalline polyester resin is preferably blended in an amount of 400 to 9900 parts by mass, and 614 to 4900 parts by mass with respect to 100 parts by mass of the specific polymer A. More preferably.
  • the polymer derived from dehydroabietic acid of the present embodiment can be suitably used as a binder for toner among the composite materials.
  • the toner of the present exemplary embodiment only needs to contain a pigment, a release agent, and a polymer derived from the dehydroabietic acid of the present exemplary embodiment. If necessary, a charge control agent, a carrier, an external additive and the like can be contained.
  • Inorganic fine powders and organic fine particles may be externally added for the purpose of imparting fluidity improvement and charge control to the toner.
  • silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These particles preferably have a number average primary particle size of 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.
  • the pigment is not limited, and either an organic pigment or an inorganic pigment can be used.
  • organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable.
  • the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is particularly preferable as the black pigment. These are preferably added to the toner in an amount of, for example, 1 to 30% by mass, preferably 5 to 20% by mass, and 30 to 85% by mass when a magnetic material is used as the black pigment.
  • the binder only needs to contain the dehydroabietic acid-derived polymer of the present embodiment, and it is more preferably added to the toner, for example, 10 to 95% by mass, and more preferably 20 to 80% by mass.
  • other commonly used binders can be used in combination.
  • olefin resins such as polyethylene and polypropylene
  • styrene resins such as polystyrene and ⁇ -polymethylstyrene
  • (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile
  • polyamide resins polycarbonate resins, polyether resins and These copolymer resins are exemplified.
  • the toner binder may be used.
  • release agent all release agents conventionally used for toners can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. The amount of these added is preferably 3 to 20% by mass, more preferably 5 to 18% by mass, in the toner.
  • the charge control agent may be added as necessary, but a colorless one is preferred from the viewpoint of color development. Examples include quaternary ammonium salt structures, calixarene structures, azo complex dyes, and the like.
  • the addition amount of the charge control agent is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass, in the toner.
  • the carrier either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin-coated carrier in which the magnetic material particle surface is coated with a resin or the like may be used.
  • the average particle size of the carrier is preferably 30 to 150 ⁇ m in terms of volume average particle size.
  • external additives examples include known particles such as silica particles whose surfaces have been hydrophobized, titanium oxide particles, alumina particles, cerium oxide particles, inorganic particles such as carbon black, and polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Can be used. Among these, two or more kinds of external additives are used, and at least one of the external additives preferably has an average primary particle diameter in the range of 30 nm to 200 nm, and more preferably in the range of 30 nm to 180 nm. .
  • the transferability can be improved by adding a large external additive having an average primary particle size of 30 nm to 200 nm.
  • the average primary particle diameter of the external additive is smaller than 30 nm, the initial toner fluidity is good, but the non-electrostatic adhesion between the toner and the photoreceptor cannot be sufficiently reduced, and the transfer efficiency is low. In some cases, image drop may occur and the image may be lost or the uniformity of the image may be deteriorated. Further, external additive particles are embedded in the toner surface due to stress in the developing device over time, and the chargeability may change, causing problems such as a decrease in copy density and fogging on the background. When the average primary particle diameter of the external additive is larger than 200 nm, it may be easily detached from the toner surface and may cause deterioration of fluidity.
  • the toner according to the exemplary embodiment preferably has an average circularity in the range of 0.960 to 0.980, and more preferably in the range of 0.960 to 0.970.
  • a spherical toner is advantageous in terms of developability and transferability, but it may be inferior to an indeterminate shape in terms of cleaning properties.
  • transfer efficiency and image density can be improved, high-quality image formation can be performed, and the surface of the photoreceptor can be improved.
  • the volume average particle size of the toner of the present embodiment is desirably 3 ⁇ m or more and 9 ⁇ m or less, more desirably 3.5 ⁇ m or more and 8.5 ⁇ m or less, and further desirably 4 ⁇ m or more and 8 ⁇ m or less. If the volume average particle diameter is 3 ⁇ m or more, a decrease in toner fluidity can be suppressed, and the chargeability of each particle can be easily maintained. In addition, the charge distribution does not spread, preventing fogging on the background and preventing toner from spilling from the developer. Further, when the volume average particle diameter of the toner is 3 ⁇ m or more, the cleaning property is improved. If the volume average particle size is 9 ⁇ m or less, a decrease in resolution can be suppressed, so that a sufficient image quality can be obtained and the recent demand for high image quality can be satisfied.
  • the volume average particle size distribution index GSDv is preferably 1.30 or less, more preferably 1.15 or more and 1.28 or less, and 1.17 or more and 1.26 or less. More preferably it is. If GSDv is larger than the above range, the sharpness and resolution of the image may decrease.
  • the number average particle size distribution index GSDp is preferably 1.30 or less. If GSDp is larger than the above range, the ratio of the small particle size toner becomes high, and electrostatic control may be difficult.
  • the volume average particle diameter D50 is, for example, a particle size range (channel) divided based on a particle size distribution measured by a measuring instrument such as Coulter Counter TAII, Multisizer II (manufactured by Beckman-Coulter).
  • the cumulative distribution is drawn from the smaller diameter side, and the particle size that becomes 16% cumulative is the volume D16v, the number D16P, the particle size that becomes the cumulative 50% is the volume D50v, the number D50P, and the particle size that becomes the cumulative 84%. Is defined as a volume D84v and a number D84P.
  • the volume average particle size distribution index (GSDv) is calculated as (D84v / D16V) 1/2 .
  • the SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of toner particles dispersed on the surface of a slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value thereof Is obtained.
  • SEM scanning electron microscope
  • the method for producing the toner according to the exemplary embodiment is not particularly limited, and a commonly used method can be applied. Among them, a step of forming toner particles by a wet manufacturing method (for example, aggregation and coalescence method, suspension polymerization method, dissolution suspension granulation method, dissolution suspension method, dissolution emulsion aggregation and aggregation method, etc.) And a step of washing.
  • a wet manufacturing method for example, aggregation and coalescence method, suspension polymerization method, dissolution suspension granulation method, dissolution suspension method, dissolution emulsion aggregation and aggregation method, etc.
  • a wet production method for producing toner particles in an aqueous medium is preferable, but an emulsion aggregation method is particularly desirable, and an emulsion aggregation method using a phase inversion emulsification method is more desirable. .
  • the emulsion aggregation method is a method of preparing dispersions (emulsion liquid, pigment dispersion liquid, etc.) each containing components (binder resin, colorant, etc.) contained in the toner, and mixing these dispersion liquids to combine the toner components.
  • aggregated particles are produced by agglomeration, and then the aggregated particles are heated to the melting point or glass transition temperature of the binder resin or higher to thermally fuse the aggregated particles.
  • the emulsion aggregation method makes it easier to produce toner with a smaller particle size and has a narrower particle size distribution compared to the dry kneading and pulverization method and other wet methods such as the melt suspension method and the dissolution suspension method. Easy to obtain. Further, the shape control is easier than in the melt suspension method, the dissolution suspension method, and the like, and a uniform amorphous toner can be produced. Further, the structure of the toner, such as film formation, is controlled, and when a release agent or a crystalline polyester resin is contained, exposure of these surfaces is suppressed, so that deterioration of chargeability and storage stability is prevented.
  • the toner for toner containing the polymer derived from dehydroabietic acid of the present embodiment is used to produce a toner by the emulsion aggregation method, the resin particle stability in the aqueous resin dispersion is good, and the particle size distribution is excellent with a small particle size. Toner is produced.
  • the details of the wet manufacturing method of the toner are disclosed in, for example, JP2009-229919A, JP2009-46559A, JP2009-151241, JP3344169A, and JP31411783A.
  • the methods described in Japanese Patent Application Laid-Open No. 2008-165017, Japanese Patent Application Laid-Open No. 2010-20170, Japanese Patent Application Laid-Open No. 2010-210959, and the like can also be suitably applied to this embodiment.
  • the image forming method to which the toner of the exemplary embodiment is applied is not particularly limited.
  • a method of forming an image after forming an image on a photoconductor to form an image or an image forming method formed on the photoconductor.
  • a method may be used in which images are sequentially transferred to an intermediate transfer member, the image is formed on the intermediate transfer member, and then transferred to an image forming member such as paper to form an image.
  • Oxalyl chloride (13 g) was added dropwise at room temperature to a mixture of dehydroabietic acid (30.0 g) and methylene chloride (60 ml). After stirring for 3 hours, the solvent was distilled off under reduced pressure, and 16 g of methanol was added dropwise thereto. After stirring at room temperature for 3 hours, excess methanol was distilled off under reduced pressure to obtain Intermediate Compound A (31 g). Intermediate compound A (31 g) and paraformaldehyde (2.1 g) were added to methylene chloride (150 ml), and sulfuric acid (50 ml) was added dropwise at 10 to 15 ° C.
  • Dehydroabietic acid (75 g) and succinic anhydride (38 g) were dissolved in methylene chloride (1 L), and anhydrous aluminum chloride (130 g) was added in small portions under ice cooling. After stirring at 10-15 ° C. for 2 hours, the reaction solution was poured into ice water. The produced white crystals were collected by filtration, washed with water, and further washed with methanol to obtain DHA-3 (72 g).
  • the glass transition point was measured under the following conditions using a differential scanning calorimeter (SII Technology, DSC6200). The measurement was performed twice on the same sample, and the second measurement result was adopted.
  • ⁇ Atmosphere in measurement chamber Nitrogen (50 mL / min)
  • Raising rate 10 ° C / min
  • Measurement start temperature 0 °C -Measurement end temperature: 200 ° C -Sample pan:
  • the obtained reaction product was taken out into a Teflon (registered trademark) heat-resistant container, and polymer P-1 (weight average molecular weight) was obtained. 21400, molecular weight distribution 3.7, glass transition point 56 ° C., acid value 13 mgKOH / g).
  • the DSC chart and Tg of the polymer P-1 were calculated. This auxiliary line is shown in FIG.
  • reaction product was taken out into a Teflon (registered trademark) processed heat-resistant container and polymer B-2 (weight average molecular weight 48,600, molecular weight distribution 6.6, glass transition point 58 ° C., acid value 13.6 mgKOH / g). )
  • (Resin C) Polyester resin raw material alcohol component 288 g, isophthalic acid 334 g raw material acid component, disproportionated rosin (acid value 157.2 mg KOH / g) 1528 g and tetra-n-butyl titanate 1.72 g (acid component and alcohol component) as reaction catalyst 0.080 parts by weight with respect to 100 parts by weight in total) was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube, and stirred in a nitrogen atmosphere. Then, the polycondensation reaction was carried out at 250 ° C. for 10 hours, and it was confirmed by a flow tester that the predetermined softening temperature was reached, and the reaction was completed. This was designated as Resin C-1.
  • cP-1 an example in which the total number of carbon atoms of G 1 in formula (I) is 3, DHA-2 (200 g), dimethyl terephthalate (141.38 g), 1,3-propanediol (163.82 g) ) And ethyl orthotitanate (250 ⁇ L) were heated and stirred at 240 ° C. for 70 minutes under a nitrogen stream, and the produced water and methanol were distilled off. Next, the temperature was raised to 260 ° C., and the mixture was heated and stirred as it was for 3 hours while distilling off the water, methanol and excess 1,3-propanediol produced as the polymerization proceeded.
  • trimellitic anhydride (9.19 g) was added, and the reaction was continued for another hour.
  • the obtained reaction product was taken out into a Teflon (registered trademark) processed heat-resistant container, and polymer cP-1 (weight average molecular weight) 13000, molecular weight distribution 3.1, glass transition point 65 ° C., acid value 13 mgKOH / g).
  • Resin dispersions A02 to A09 and Comparative Examples Dispersions Ac1 and Ac2 Resin dispersions A02 to A09, Ac1 were prepared in the same manner as in the preparation of resin dispersion A01, except that the resin used was changed to resin A shown in Table 1 (comparative example c12 was cP-1). Ac2 was obtained.
  • Resin dispersions B-1, B-2, and C-1 were prepared in the same manner as in the preparation of the resin dispersion A01, except that the resins used were changed to resins B-1, B-2, and C-1, respectively. -1 was obtained.
  • the obtained crystalline polyester resin (I) had a weight average molecular weight of 25,000 and a number average molecular weight of 5,800. Further, when the melting point (Tm) of the crystalline polyester resin (I) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 75 ° C. there were.
  • Tm melting point
  • -Crystalline polyester resin (I) 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 2.0 parts by mass-Ion exchange water: 210 parts by mass
  • the above is mixed and heated to 100 ° C
  • the dispersion was heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size was 0.15 ⁇ m, and the solid content was 30% by mass.
  • a crystalline polyester resin dispersion (I) was obtained.
  • the obtained crystalline polyester resin (II) had a weight average molecular weight of 22,000 and a number average molecular weight of 4400. Further, when the melting point (Tm) of the crystalline polyester resin (II) was measured using a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 72 ° C. there were.
  • -Crystalline polyester resin (II) 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 1.8 parts by mass-Ion exchange water: 210 parts by mass or more mixed and heated to 100 ° C Then, after dispersion with IKA Ultra Turrax T50, the dispersion is heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size is 0.14 ⁇ m, and the solid content is 30% by mass. A crystalline polyester resin dispersion (II) was obtained.
  • Example 1 and Comparative Example 1> Using the DHA resin dispersion, the resin B dispersion, and the like, toners and developers were prepared and evaluated using the colorant dispersion and the release agent dispersion prepared as follows. The results are shown in the table below.
  • Cyan pigment (Daiichi Seika Co., Ltd., Pigment Blue 15: 3, copper phthalocyanine) (100 parts by mass), anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) (10 parts by mass) and ion-exchanged water (350 Parts by weight) were mixed and dispersed for 1 hour with a high-pressure impact disperser (HJP 30006, manufactured by Sugino Machine Co., Ltd.) to obtain a cyan colorant dispersion.
  • HJP 30006 high-pressure impact disperser
  • Paraffin wax HNP-9: Nippon Seiwa Co., Ltd.
  • anionic surfactant Neogen R 6 parts by mass
  • ion-exchanged water 200 parts by mass
  • the said colorant dispersion (60 mass parts) and the said mold release agent dispersion (80 mass parts) were added, and it stirred for 5 minutes. Further, 1% nitric acid was added little by little to adjust the pH to 3.0. Thereafter, polyaluminum chloride (0.4 parts by mass) was added, and when the temperature was raised to 50 ° C., 180 parts of a resin dispersion was added. After stirring for 30 minutes, a 5% by mass aqueous sodium hydroxide solution was added to adjust the pH to 9.0. Subsequently, the temperature was raised to 90 ° C., stirred at 90 ° C. for 3 hours, and then cooled to obtain a toner dispersion 101b.
  • the toner particle dispersion obtained above was filtered and washed with ion-exchanged water.
  • the toner particles were again dispersed in ion exchange water, filtered and washed. This operation was further repeated twice, and then the pH of the toner particle dispersion was adjusted to 4.0 with 1% nitric acid.
  • the toner particles were filtered, washed with ion-exchanged water until the electric conductivity of the filtrate was 15 ⁇ S / cm or less, and then dried under reduced pressure in an oven at 40 ° C. for 5 hours to obtain toner particles.
  • the toner 101 was obtained by sieving with a vibrating sieve having an opening of 45 ⁇ m.
  • Test toners 102 to 109, c11, and c12 were prepared in the same manner as in the preparation of the toner 101 except that the types and blends of the specific polymer and crystalline polymer used were changed as shown in the table below.
  • Silicon resin (SR2411 manufactured by Toray Dow Corning) (300 parts by mass), toluene (1200 parts by mass) and ferrite core material (5 kg) having an average particle size of 50 ⁇ m are placed in a rotating disk type fluidized bed coating apparatus, and the surface of ferrite is coated Covered with silicone resin. Subsequently, the coating was taken out and heated at 250 ° C. for 2 hours, and the coating film was aged to prepare a carrier.
  • Silicon resin SR2411 manufactured by Toray Dow Corning
  • the toner and carrier were mixed so that the toner concentration was 5% by mass and the total amount was 1 kg to obtain a developer.
  • the average particle diameter (volume average particle diameter, median diameter) of the resin dispersion was measured using a laser diffraction type particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.) and evaluated according to the following evaluation criteria.
  • C The average particle size was 300 nm or more and less than 800 nm.
  • D The average particle size was 800 nm or more, or measurement was impossible.
  • the glossiness of the solid part was measured using the gloss meter by Murakami Color Material Co., Ltd. In the measurement, the incident light density incident at an angle of 45 degrees with respect to the image surface and the reflected light density at 135 degrees were measured for each temperature, and the ratio of the reflected light density to the incident light density was defined as the glossiness. A glossiness of 50% or more is preferable because it has suitability for color high-quality images. Further, regarding the uneven glossiness of the fixed image, the uneven glossiness of the solid image portion was visually evaluated based on the following criteria. A: Unevenness is not confirmed B: Obvious unevenness is confirmed
  • the resin composition (Example) of the present invention has high uniformity and is suitable as a toner material. It can also be seen that when used as a toner, an image with high quality and excellent fixability can be formed.
  • the resin of the present invention uses a plant-derived compound and contributes to the preservation of the global environment.
  • the comparative example (c11) does not contain the resin B, the compatibility with the crystalline resin is poor, and fixing, image quality, and image strength are insufficient.
  • the molecular weight of the resin B it can be seen that the image strength is increased by using the high molecular weight resin (B-2).
  • Example 2 Each test was performed in the same manner except that P-1 used in test 101 was changed as shown in the table below. As a result, in each test body, a “Good” result was obtained in each test. Hot offset: 190 ° C or higher ... Good Glossiness: 75 or more ... Good Glossiness unevenness: A in the above evaluation ... Good Other than that ... Bad
  • Photoconductor (latent image carrier) 1 Photoconductor (latent image carrier) 2 Toner supply chamber 3 Drum 4 Paper 5 Toner 51 Transfer image 7 Cleaner 8 Charging means 9 Static eliminator L Exposure

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Abstract

La présente invention concerne une composition de résine comprenant : une résine (A) contenant des unités structurales représentées par la formule (I) et des unités répétitives contenant un squelette issu de l'acide déshydroabiétique dans la chaîne principale; et une résine (B) contenant des unités structurales représentées par la formule (IIa). (Dans la formule (I), G1 représente un groupe de liaison alcane en C4 ou plus ou un groupe de liaison alcène; et X, Y et Z sont chacun indépendamment un groupe de liaison bivalent). (Dans la formule (IIa), R1 représente un substituant; X2 représente un groupe de liaison bivalent ou une simple liaison; G représente un groupe de liaison bivalent; n1 représente un entier 0-4; nb représente un entier 0-3, ∗ représente une liaison atomique incorporée dans la chaîne principale; et le cycle Ar représente un groupe de liaison aryle).
PCT/JP2012/072470 2011-09-16 2012-09-04 Composition de résine et son procédé de fabrication, et toner l'utilisant Ceased WO2013038955A1 (fr)

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JP5797537B2 (ja) * 2010-12-21 2015-10-21 富士フイルム株式会社 デヒドロアビエチン酸誘導体の位置異性体混合物の製造方法
JP6871766B2 (ja) * 2017-03-10 2021-05-12 株式会社東芝 画像形成装置及び画像形成方法

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JPH01201675A (ja) * 1988-02-08 1989-08-14 Nippon Synthetic Chem Ind Co Ltd:The トナー組成物
JP2008308562A (ja) * 2007-06-14 2008-12-25 Unitika Ltd 生分解性ポリエステル樹脂組成物、その製造方法、それを用いた成形体
JP2010020170A (ja) * 2008-07-11 2010-01-28 Japan U-Pica Co Ltd トナー用ポリエステル樹脂及び静電荷現像用トナー
JP2011107341A (ja) * 2009-11-16 2011-06-02 Kao Corp トナー用結着樹脂の製造方法
WO2011096145A1 (fr) * 2010-02-08 2011-08-11 富士フイルム株式会社 Polymère d'acide déshydroabiétique, produits moulés, procédé pour la production de polymère d'acide déshydroabiétique, et composé d'acide déshydroabiétique

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JP5398650B2 (ja) * 2009-06-25 2014-01-29 富士フイルム株式会社 新規なデヒドロアビエチン酸重合体
JP5300680B2 (ja) * 2009-09-30 2013-09-25 富士フイルム株式会社 新規なアビエタン重合体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01201675A (ja) * 1988-02-08 1989-08-14 Nippon Synthetic Chem Ind Co Ltd:The トナー組成物
JP2008308562A (ja) * 2007-06-14 2008-12-25 Unitika Ltd 生分解性ポリエステル樹脂組成物、その製造方法、それを用いた成形体
JP2010020170A (ja) * 2008-07-11 2010-01-28 Japan U-Pica Co Ltd トナー用ポリエステル樹脂及び静電荷現像用トナー
JP2011107341A (ja) * 2009-11-16 2011-06-02 Kao Corp トナー用結着樹脂の製造方法
WO2011096145A1 (fr) * 2010-02-08 2011-08-11 富士フイルム株式会社 Polymère d'acide déshydroabiétique, produits moulés, procédé pour la production de polymère d'acide déshydroabiétique, et composé d'acide déshydroabiétique

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