WO2016002813A1 - Method for inhibiting agglomeration of powder - Google Patents

Method for inhibiting agglomeration of powder Download PDF

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Publication number
WO2016002813A1
WO2016002813A1 PCT/JP2015/068908 JP2015068908W WO2016002813A1 WO 2016002813 A1 WO2016002813 A1 WO 2016002813A1 JP 2015068908 W JP2015068908 W JP 2015068908W WO 2016002813 A1 WO2016002813 A1 WO 2016002813A1
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Prior art keywords
powder
dye
resin
dyes
resin composition
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PCT/JP2015/068908
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French (fr)
Japanese (ja)
Inventor
諒 寺西
慎介 清水
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日本化薬株式会社
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Priority to JP2016531408A priority Critical patent/JPWO2016002813A1/en
Publication of WO2016002813A1 publication Critical patent/WO2016002813A1/en

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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
    • 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
    • G03G9/09—Colouring agents 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
    • G03G9/097—Plasticisers; Charge controlling agents

Definitions

  • the present invention relates to a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye.
  • the powder of the resin composition containing the dye is, for example, as a coloring material, various inks such as ultraviolet curable ink, thermosetting ink, inkjet ink, gravure ink, offset ink, liquid toner, transfer type silver halide photosensitive material. It is used in various fields such as thermal transfer recording materials, recording pens, optical recording medium materials, adhesives, powder paints, powder toners and the like. Examples of the colorant contained in these powders include various pigments and dyes. However, the resin composition powder containing a disperse dye or oil-soluble dye as a colorant is different from other colorants, for example, during transportation, when used as a coloring material, due to long-term storage or change over time, etc.
  • Patent Document 1 discloses a colorant fine particle dispersion prepared from a hydrophobic colorant selected from oil-soluble dyes and disperse dyes and a rosin compound that is a natural resin, as a raw material for water-based inkjet recording inks. Further, as dry powder toners and liquid toners used in the electrophotographic method, for example, Patent Documents 2 to 5 disclose various types. Sublimation transfer dyeing using an electrophotographic method is disclosed, for example, in Patent Documents 6 to 10 below.
  • JP-A-8-34941 JP 2012-1829 A Japanese Patent Laid-Open No. 5-27474 Japanese Unexamined Patent Publication No. 9-73198 Japanese Patent Laid-Open No. 3-18866 Japanese Patent Laid-Open No. 02-295787 Japanese Patent Laid-Open No. 06-055991 Japanese Patent Laid-Open No. 10-058638 JP 2000-029238 A Special Table 2006-500602
  • An object of the present invention is to provide a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye.
  • the inventors of the present invention have said resin solubility parameter (Solubility Parameter, hereinafter referred to as “SP value”) in a resin composition powder containing at least a resin and a dye. ) was set to 9.5 or more, and the present invention was completed by finding that the above-mentioned problems could be solved. That is, the present invention relates to the following 1) to 10).
  • SP value Solubility Parameter
  • Powder of; 4) The method for suppressing powder aggregation according to 1) above, wherein the powder of the resin composition containing at least a resin and a dye is a toner further containing at least a wax, a charge control agent, and an external additive; 5) The method for suppressing powder aggregation according to 4) above, wherein the dye is a disperse dye and / or a solvent dye; 6) A toner for use in the method for suppressing powder aggregation described in 5) above, which contains at least a resin, a dye, a wax, a charge control agent, and an external additive; 7) A powder of a resin composition containing at least a resin and a dye, A powder having an SP value of 9.5 or more; 8) A toner containing at least a resin, a dye, a wax, a charge control agent and an external additive, A toner having an SP value of 9.5 or more; 9) mixing at least a resin and a dye to obtain a resin-dye mixture; A
  • a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye can be provided.
  • the “powder” of the resin composition is used to include all powders having various shapes such as particles.
  • “%” and “part” are described on a mass basis, including examples.
  • the unit of the SP value is “(cal / cm 3 ) 1/2 ”.
  • the powder of the resin composition contains at least a resin having an SP value of 9.5 or more.
  • the powder of the resin composition may contain only a resin having an SP value of 9.5 or higher, or a resin having an SP value of 9.5 or higher and other resins may be used in combination.
  • limit especially as resin with SP value 9.5 or more Polyester is preferable.
  • styrene-type copolymer examples thereof include, for example, a polymer of styrene or a styrene derivative, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane. , Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. In these, a styrene-type copolymer is preferable.
  • any of the above-described resins may be used alone or in combination of two or more.
  • polyester resins it is preferable to use polyester resins together.
  • the SP value of the resin is usually 9.5 or more, preferably 9.5 to 15.0, more preferably 9.5 to 12.0, and even more preferably 9 0.5 to 11.0, particularly preferably 9.8 to 10.4.
  • styrene or styrene derivative polymer examples include polystyrene, poly p-chlorostyrene, and polyvinyltoluene.
  • styrene copolymer examples include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-acrylic acid ester copolymer.
  • Polymers (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer ( Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, etc.), styrene- ⁇ -chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ketone copolymer, styrene-butadiene Polymers, styrene - isoprene copolymer, styrene - acrylonit
  • Examples of commercially available products of the above resins include Diacron FC-684, Diacron FC-2232, Diacron FC-1224, Diacron FC-316, Diacron ER-508, etc. manufactured by Mitsubishi Rayon Co., Ltd., known as polyester. And CPR-100, CPR-250, and CPR-390 manufactured by Mitsui Chemicals, Inc., which are known as styrene-acrylic acid ester copolymers.
  • the SP value is disclosed in “K.W. Suh, J.M. Corbett, J.Appl.Poly.Sci., Vol.12, p.2359-2370 (1968)”.
  • the value obtained from the result of the cloud point titration method uses a poor solvent (n-hexane) with a low SP value and a poor solvent (deionized water) with a high SP value in a solution of 0.5 g of resin dissolved in T ml of THF (tetrahydrofuran). The amount of dripping of the poor solvent required until dropping and turbidity are measured. From the drop amounts of n-hexane and deionized water obtained from the measurement, the SP value can be calculated by the following formula.
  • V H H / (T + H).
  • V D D / (T + D).
  • ⁇ ml ⁇ T ⁇ T / (T + H) + ⁇ H ⁇ H / (T + H).
  • [delta] mh [delta] T * T / (T + D) + [delta] D * D / (T + D).
  • V H Volume fraction of n-hexane.
  • V D Volume fraction of deionized water
  • ⁇ ml SP value of n-hexane / THF mixed solution.
  • ⁇ mh SP value of deionized water / THF mixed solution.
  • T The amount of THF required to dissolve the resin (ml).
  • H Drip amount of n-hexane (ml).
  • D Drip amount of deionized water (ml).
  • the dye contained in the powder of the above resin composition is not particularly limited, and includes, for example, water-soluble dyes such as reactive dyes, direct dyes, acid dyes, metal complex hydrochloric acid dyes or mordant dyes; and disperse dyes and bases.
  • Water-insoluble dyes such as oil-soluble dyes such as water-soluble dyes, vat dyes, and solvent dyes. Among these, water-insoluble dyes are preferable, and disperse dyes and / or solvent dyes are more preferable.
  • the “water-insoluble dye” means a dye that is insoluble or hardly soluble in water.
  • “Slightly soluble” in water means a dye having a solubility in water at 25 ° C. of usually 0.11 g / liter or less, preferably 0.01 g / liter or less, more preferably 0.001 g / liter or less.
  • reactive dyes include C.I. I. Yellow dyes such as Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102; I. Orange dyes such as Reactive Orange 5, 9, 12, 13, 35, 45, 99; I. Brown dyes such as Reactive Brown 2, 8, 9, 17, 33; I. Red dyes such as Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245; I. Violet dyes such as Reactive Violet 1, 24; I. Blue dyes such as Reactive Blue 2, 5, 10, 13, 14, 15, 15: 1, 49, 63, 71, 72, 75, 162, 176; I. Green dyes such as Reactive Green 5, 8, 19; I. And black dyes such as Reactive Black 1, 8, 23, 39; and the like.
  • Yellow dyes such as Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102
  • Orange dyes such as Reactive Orange 5, 9, 12, 13, 35, 45, 99
  • I. Brown dyes such as Reactive Brown 2, 8, 9, 17,
  • direct dyes include C.I. I. Yellow dyes such as Direct Yellow 4, 5, 11, 12, 50, 86, 87, 127, 130, 132, 142, 147, 153; I. Orange dyes such as Direct Orange 15, 34, 39, 102; I. Brown dyes such as Direct Brown 195, 209, 210; I. Red dyes such as Direct Red 81, 89, 224, 225, 226, 227, 239, 243, 252, 255; I. Violet dyes such as Direct Violet 9, 51, 66; I. Blue Blue such as Direct Blue 86, 87, 108, 199, 200, 202, 218, 237, 248, 267, 273, 279, 281; I. Direct Green 59, 80 and other green dyes; C.I. I. Direct Black 19, 22, 112, 117, 161, 170, 171 and the like; and the like.
  • acid dyes include C.I. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 72, 73, 79, Yellow dyes such as 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246; I.
  • Violet dyes such as Acid Violet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126; I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, Blue dyes such as 239, 249, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350; I.
  • metal complex hydrochloric acid dyes include C.I. I. Acid Yellow 59, 111, 112, 116, 161 etc. yellow dyes; C.I. I. Acid Orange 82, 87, 88, 95, 122, 147 and other orange dyes; C.I. I. Acid Red 209, 211, 215, 216, 217, 256, 262, 317, 355 and other red dyes; I. Violet dyes such as Acid Violet 66, 75, 116; I. Acid Blue 167, 168, 171, 234, 250, 276 and other blue dyes; I.
  • Brown dyes such as Acid Brown 30, 44, 45, 46, 224, 282, 283, 294, 295, 296, 297, 333, 352, 353, 369, 368;
  • C.I. I. A black dye such as Acid Black 52: 1, 107, 110, 132, 155, 179;
  • mordant dyes include C.I. I. Yellow Yellow, such as Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 50, 56, 61, 62, 65; I. Orange dyes such as Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, Red dyes such as 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; I.
  • Yellow Yellow Yellow such as Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 50, 56, 61, 62, 65
  • Orange dyes such as Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48
  • Violet dyes such as Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; I. Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, Blue dyes such as 48, 49, 53, 61, 74, 77, 83, 84; I. Green Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc .;
  • basic dyes include C.I. I. Yellow dyes such as Basic Yellow 1, 2, 11, 28, 51, 57, 87; I. Orange dyes such as Basic Orange 2, 14, 21, 24, 31; I. C. Brown Brown 1, 16, 17, etc. brown dyes; I. Red dyes such as Basic Red 1, 2, 5, 9, 12, 13, 14, 15, 18, 22, 27, 29, 35, 36, 40, 51, 76, 118; I. Violet dyes such as Basic Violet 1, 2, 3, 4, 7, 10, 14, 15, 20, 27; I. Blue dyes such as Basic Blue 1, 3, 5, 7, 9, 16, 22, 24, 25, 26, 28, 29, 64, 99, 117; I. Basic Green 1, 4, 5, etc. green dyes; C.I. I. Black dyes such as Basic Black 2;
  • vat dyes include C.I. I. Yellow dyes such as Vat Yellow 2, 4, 10, 20, 33; I. Orange dyes such as Vat Orange 1, 2, 3, 5, 7, 9, 13, 15; I. Red dyes such as Vat Red 1, 2, 10, 13, 15, 16, 41, 61; I. Violet dyes such as Vat Violet 1, 2, 9, 13, 21; I. Blue dyes such as Vat Blue 1, 3, 4, 5, 6, 8, 12, 14, 18, 19, 20, 29, 35, 41; I. Green dyes such as Vat Green 1, 2, 3, 4, 8, 9; I. Brown dyes such as Vat Brown 1, 3, 25, 44, 46; I. And black dyes such as Vat Black 1, 8, 9, 13, 14, 20, 25, 27, 29, 36, 56, 57, 59, 60;
  • disperse dyes include C.I. I. Disperse Yellow 3, 4, 5, 7, 8, 9, 13, 23, 24, 30, 33, 34, 39, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 200, 202, 204, 210, 211, 215, 216, 218, Yellow dyes such as 224 and 237; I.
  • solvent dyes include C.I. I. Solvent Yellow 9, 17, 19, 21, 24, 31, 35, 43, 44, 58, 61, 80, 93, 100, 102, 103, 105, 112, 114, 162, 163, etc .; C.I. I. Orange dyes such as Solvent Orange 1, 67; I. Red dyes such as Solve Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, 146; I. Violet dyes such as Solvent Violet 8, 21; I. Blue dyes such as Solvent Blue 2, 11, 25, 36, 55, 63, 83, 105, 111; I. Green dyes such as Solvent Green 3; I. Brown dyes such as Solvent Brown 3; C.I. I. And Black dyes such as Solvent Black 3, 5, 7, 22, 27, 29;
  • any of the above dyes can be used alone. Further, two or more kinds can be used in combination for the purpose of obtaining a desired color tone. For example, in the preparation of a black ink, a blue dye as a main component, an orange dye and a red dye can be appropriately blended to adjust a black color, and this can be used as a black dye. For example, a plurality of dyes can be blended depending on the purpose of finely adjusting the color tone such as blue, orange, red, violet, or black to a desired color tone.
  • the powder of the resin composition containing a disperse dye or a solvent dye tends to cause powder aggregation.
  • disperse dyes and solvent dyes dyes having sublimation properties are more likely to cause powder aggregation.
  • the effect of suppressing the aggregation of the powder of the present invention is exhibited extremely well in the powder of the resin composition containing these dyes.
  • a dye having sublimation property means “a dyeing fastness test method for dry heat treatment [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by the Japanese Standards Association). ”Indicates a dye having a heat treatment test (Method C) contamination (polyester) of a quaternary grade or lower, preferably a quaternary grade close to 3.5 or a tertiary grade, more preferably a tertiary grade or less. . That is, in the present specification, the dye having a quaternary test result of the heat-sensitive test (Method C) contamination (polyester) is included in the dye suitable for sublimation transfer.
  • Method C heat treatment test
  • the dye having a quaternary test result of the heat-sensitive test (Method C) contamination (polyester) is included in the dye suitable for sublimation transfer.
  • examples of known dyes include the following dyes.
  • yellow dyes include C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; I. Solvent Yellow 43, 114, 163; and the like.
  • orange dyes include C.I. I. Disperse Orange 1, 1: 1, 5, 20, 25, 25: 1, 33, 56, 76; and the like.
  • brown dye include C.I. I. Disperse Brown 2; etc.
  • red dyes include C.I. I. Disperse Red 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240; I.
  • Examples of the violet dye include C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57;
  • Examples of blue dyes include C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360; I. Solvent Blue 3, 63, 83, 105, 111; and the like.
  • the standard is usually 1 to 40%, preferably 2 to 35%, more preferably 3 to 25% with respect to the total mass of the powder.
  • the use of the resin composition powder is not particularly limited.
  • a coloring material contained in a printing ink or liquid toner such as an ultraviolet curable ink, a thermosetting ink, an inkjet ink, a gravure ink, or an offset ink;
  • Examples include silver halide photosensitive materials; thermal transfer recording materials; coloring materials containing recording pens, optical recording medium materials, adhesives, etc .; coloring materials containing powder paints, powder toners, etc. .
  • coloring materials contained in printing inks and liquid toners such as ultraviolet curable inks, thermosetting inks, inkjet inks, gravure inks and offset inks; powder paints, powder toners, etc.
  • are preferable and examples thereof include powdered colored resin compositions, powder paints, and powder toners contained in liquid toners.
  • the powder of the resin composition can be used for various applications as described above.
  • the powder of this resin composition may contain additives other than resin according to the use application.
  • powder toner may be mentioned, for example, additives such as wax, charge control agent, and external additive. These types, the content of the resin composition in the total mass of the powder, and the production method of the powder toner containing these additives are all described in known prior art documents.
  • the powder of the resin composition When the powder of the resin composition is used as a powder toner, it may be prepared as a powder toner based on known prior art documents, and may be prepared in the same manner when used for other purposes. Even if the powder of the said resin composition contains such an additive, the sufficient aggregation inhibitory effect is exhibited.
  • the volume average particle diameter (D50 Vol.) Of the powder of the resin composition is not particularly limited, and may be an appropriate particle diameter depending on the purpose and / or application.
  • the powder of the above resin composition is usually 1 ⁇ m to 12 ⁇ m, preferably 2 ⁇ m to 10 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m, and further preferably about 5 ⁇ m to 8 ⁇ m.
  • the average particle size is measured using a precision particle size distribution analyzer (manufactured by Beckman Coulter, Ltd., Multisizer 4). Unless otherwise specified, the average particle size is rounded off to the nearest decimal point. .
  • the powder of the above resin composition As a method for producing the powder of the above resin composition, at least a resin and a dye are kneaded and then pulverized and classified; a polymerizable monomer is polymerized in the presence of a dye such as a sublimation dye
  • a polymerization method for example, an emulsion polymerization method, a dissolution suspension method, an emulsion association method, a polyester stretching method, etc.
  • the pulverization method is preferable in that the powder of the resin composition can be produced at high speed, and the polymerization method is preferable in that the volume average particle diameter of the powder is reduced.
  • the production of the resin composition powder by the pulverization method can be performed, for example, by the following three steps of production steps 1 to 3.
  • [Manufacturing process 1] A step of mixing at least a polyester resin and a sublimation dye with a mixer such as a Henschel mixer to obtain a resin-dye mixture.
  • [Manufacturing process 2] A step of melt-kneading the resin-dye mixture obtained in the production step 1 with a closed kneader; or a monoaxial or biaxial extruder; etc., and cooling to obtain a resin composition.
  • the resin composition obtained in the production process 2 is roughly pulverized with a hammer mill or the like and then finely pulverized with a jet mill or the like so that a desired particle size distribution can be obtained using various classifiers and cyclones as necessary.
  • the method for suppressing powder aggregation according to the present invention can suppress the phenomenon that the dye appears on the surface of the powder of the resin composition, especially during transportation at high temperature, during use, or during storage. For this reason, it is possible to suppress the powder aggregation of the resin composition, and it is possible to provide a high-quality resin composition powder that has extremely high heat stability and stability over time and can be applied to various applications.
  • the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
  • the average particle size was measured using a precision particle size distribution measuring apparatus “Multisizer 4 (manufactured by Beckman Coulter, Inc.)”.
  • the mixer used in each preparation example is BM-RS08 manufactured by ZOJIRUSHI CORP.
  • Example 1 Preparation of resin composition powder Diacron FC-316 (91 parts) manufactured by Mitsubishi Rayon Co., Ltd., Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow) 54: 4.5 parts), and a dye (4.5 parts) represented by the following formula (1) was melt blended on a hot plate heated to 200 ° C. After cooling, the resulting kneaded product was pulverized with a mixer to obtain a resin composition powder.
  • the dye represented by the following formula (1) was synthesized by the method described in JP-A-6-184481.
  • Example 2 Preparation of resin composition powder Diacron FC-316 (90 parts) manufactured by Mitsubishi Rayon Co., Ltd., C.I. I. Disperse Blue 359 (6 parts) and a dye represented by the following formula (2) (4 parts) were melt blended on a hot plate heated to 200 ° C. After cooling, the resulting kneaded product was pulverized with a juicer mixer to obtain a powder of the resin composition of the present invention.
  • the dye represented by the following formula (2) was synthesized by the method described in JP-A-6-228444.
  • Example 3 Preparation of resin composition powder The same procedure as in Example 1 was used except that Diacron FC-2247 manufactured by Mitsubishi Rayon Co., Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Thus, a powder of the resin composition was obtained.
  • Example 4 Preparation of resin composition powder The same procedure as in Example 2 was used, except that Diacron FC-2247 manufactured by Mitsubishi Rayon Co., Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Thus, a powder of the resin composition was obtained.
  • Comparative Example 1 Preparation of Comparative Resin Composition Powder Example 1 except that Almatex CPR-390 manufactured by Mitsui Chemicals, Inc. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. In the same manner, a powder of a comparative resin composition was obtained.
  • a powder toner was prepared, and the effect of suppressing the aggregation was tested.
  • Example 5 (Process 1) Mitsubishi Rayon Co., Ltd. Diacron FC-316 (100 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5 parts), represented by the above formula (1) Dye (5 parts), Bontron E-84 (1 part) and Carnauba wax C1 (4 parts) were placed in a Henschel mixer, premixed for 10 minutes at a rotational speed of 30 m / sec, and then melt-kneaded by a twin screw extruder. did. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.8 ⁇ m.
  • Example 6 (Process 1) Mitsubishi Rayon Co., Ltd. Diacron FC-316 (96 parts), C.I. I. Disperse Blue 359 (8 parts), dye represented by the above formula (2) (6 parts), Bontron E-84 (1 part) and carnauba wax C1 (4 parts) were placed in a Henschel mixer and rotated at 30 m / sec. After premixing at a speed for 10 minutes, the mixture was melt-kneaded by a twin screw extruder. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.9 ⁇ m.
  • Condition 2 Place in a thermostat at 40 ° C ⁇ 1 ° C and store for 24 hours.
  • Condition 3 Place in a thermostat at 50 ° C. ⁇ 1 ° C. and store for 24 hours.
  • Condition 4 Place in a thermostat at 60 ° C. ⁇ 1 ° C. and store for 24 hours.
  • the resin composition powder of the present invention has an effect of suppressing bleed-out at high temperatures. Further, as is apparent from Table 2, the powder toner of the present invention has reduced powder aggregation from both aspects of aggregation and formation of aggregates, and has an effect of suppressing powder aggregation. It became clear. As the bleed-out evaluation result deteriorated from A to D, the cohesiveness and the state of the aggregate also deteriorated, and it was confirmed that there is a correlation between the bleed-out and the cohesiveness.
  • Example 7 Preparation of resin composition powder In the same manner as in Example 1 except that FC-2232 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
  • Example 8 Preparation of resin composition powder In the same manner as in Example 2 except that FC-2232 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
  • Example 9 Preparation of resin composition powder In the same manner as in Example 1 except that M-325 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
  • Example 10 Preparation of resin composition powder In the same manner as in Example 2 except that M-325 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
  • Comparative Example 8 Preparation of Comparative Resin Composition Powder Example 2 was used except that SB-370 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Similarly, a resin composition powder for comparison was obtained.
  • the method for suppressing powder aggregation of the present invention is extremely useful because it can suppress aggregation of powder of a resin composition containing a dye that can be used in various applications.

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Abstract

[Problem] The present invention addresses the problem of providing a method for preventing agglomeration of powder of a resin composition containing at least a resin and a dye. [Solution] The present invention is capable of providing a method for inhibiting agglomeration of powder of a resin composition containing at least a resin and a dye, the resin having an SP value of 9.5 or more, and thereby inhibiting powder agglomeration even during high temperature heating.

Description

粉体凝集の抑制方法Method for suppressing powder aggregation
　本発明は、少なくとも樹脂及び染料を含有する樹脂組成物の粉体における、粉体凝集の抑制方法に関する。 The present invention relates to a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye.
　染料を含有する樹脂組成物の粉体は、例えば着色材料として、紫外線硬化型インキ、熱硬化型インキ、インクジェットインキ、グラビアインキ、オフセットインキ等の各種インク、液体トナー、転写式ハロゲン化銀感光材料、感熱転写方式の記録材料、記録ペン、光記録媒体材料、接着剤、粉体塗料、粉体トナー等の様々な分野で用いられている。
　これらの粉体が含有する着色剤としては、各種の顔料や染料が挙げられる。しかしながら、着色剤として分散染料若しくは油溶性染料を含有する樹脂組成物の粉体は、他の着色剤とは異なり、例えば輸送時、着色材料としての使用時、長期の保存又は経時変化等により、特に高温下での粉体凝集が特徴的に生じることが知られてきたため、その抑制が極めて重大な課題となっている。
　この粉体凝集は、樹脂組成物中において均一に溶融又は分散していた染料が、おそらく熱により不均一化し、樹脂組成物の表面に出てしまうことにより、この表面に出た染料間の物理的又は化学的な相互作用によって生じることが示唆された。このような凝集が生じると、粉体の流動性、分散性、又は帯電性等の諸物性を損なうことに繋がるため、粉体凝集の抑制が強く要求されている。 The powder of the resin composition containing the dye is, for example, as a coloring material, various inks such as ultraviolet curable ink, thermosetting ink, inkjet ink, gravure ink, offset ink, liquid toner, transfer type silver halide photosensitive material. It is used in various fields such as thermal transfer recording materials, recording pens, optical recording medium materials, adhesives, powder paints, powder toners and the like.
Examples of the colorant contained in these powders include various pigments and dyes. However, the resin composition powder containing a disperse dye or oil-soluble dye as a colorant is different from other colorants, for example, during transportation, when used as a coloring material, due to long-term storage or change over time, etc. In particular, since it has been known that powder agglomeration occurs at high temperatures, the suppression thereof is an extremely important issue.
This powder agglomeration is caused by the fact that the dye that has been uniformly melted or dispersed in the resin composition is likely to become non-uniform due to heat and come out on the surface of the resin composition. It was suggested that it is caused by chemical or chemical interaction. When such agglomeration occurs, various physical properties such as the fluidity, dispersibility, and charging property of the powder are impaired. Therefore, suppression of the agglomeration is strongly demanded.
　特許文献１には、水性インクジェット記録用インクの原料として、油溶性染料、分散染料から選ばれる疎水性着色剤と天然樹脂であるロジン化合物から作製される着色剤微粒子分散液が開示されている。
　また、電子写真方式で用いる乾式の粉体トナーや液体トナーとしては、例えば、特許文献２～５に様々な種類のものが開示されている。
　電子写真方式を用いる昇華転写染色は、例えば下記の特許文献６～１０に開示されている。 Patent Document 1 discloses a colorant fine particle dispersion prepared from a hydrophobic colorant selected from oil-soluble dyes and disperse dyes and a rosin compound that is a natural resin, as a raw material for water-based inkjet recording inks.
Further, as dry powder toners and liquid toners used in the electrophotographic method, for example, Patent Documents 2 to 5 disclose various types.
Sublimation transfer dyeing using an electrophotographic method is disclosed, for example, in Patent Documents 6 to 10 below.
特開平８－３４９４１号公報JP-A-8-34941 特開２０１２－１８２９号公報JP 2012-1829 A 特開平５－２７４７４号公報Japanese Patent Laid-Open No. 5-27474 特開平９－７３１９８号公報Japanese Unexamined Patent Publication No. 9-73198 特開平３－１８８６６号公報Japanese Patent Laid-Open No. 3-18866 特開平０２－２９５７８７号公報Japanese Patent Laid-Open No. 02-295787 特開平０６－０５１５９１号公報Japanese Patent Laid-Open No. 06-055991 特開平１０－０５８６３８号公報Japanese Patent Laid-Open No. 10-058638 特開２０００－０２９２３８号公報JP 2000-029238 A 特表２００６－５００６０２号公報Special Table 2006-500602
　本発明は、少なくとも樹脂及び染料を含有する樹脂組成物の粉体における、粉体凝集を抑制する方法の提供を課題とする。 An object of the present invention is to provide a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye.
　本発明者らは上記課題を解決すべく鋭意研究を行った結果、少なくとも樹脂及び染料を含有する樹脂組成物の粉体において、前記樹脂の溶解性パラメータ（Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒ、以下「ＳＰ値」という。）を９．５以上とすることにより、上記の課題を解決できることを見出して本発明を完成させた。すなわち本発明は、以下の１）～１０）に関する。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have said resin solubility parameter (Solubility Parameter, hereinafter referred to as “SP value”) in a resin composition powder containing at least a resin and a dye. ) Was set to 9.5 or more, and the present invention was completed by finding that the above-mentioned problems could be solved. That is, the present invention relates to the following 1) to 10).
　１）少なくとも樹脂、及び染料を含有する樹脂組成物の粉体における、粉体凝集の抑制方法であって、該樹脂のＳＰ値が９．５以上である、粉体凝集の抑制方法;
　２）上記染料が、分散染料及び／又は溶剤染料である、上記１）に記載の粉体凝集の抑制方法；
　３）上記１）に記載の粉体凝集の抑制方法に用いる樹脂組成物の粉体であって、少なくとも樹脂、及び染料を含有し、該樹脂のＳＰ値が９．５以上である樹脂組成物の紛体；
　４）少なくとも樹脂、及び染料を含有する樹脂組成物の粉体が、さらにワックス、荷電制御剤、及び外添剤を少なくとも含有するトナーである、上記１）に記載の粉体凝集の抑制方法；
　５）上記染料が、分散染料及び／又は溶剤染料である、上記４）に記載の粉体凝集の抑制方法；
　６）上記５）に記載の粉体凝集の抑制方法に用いるトナーであって、少なくとも樹脂、染料、ワックス、荷電制御剤、及び外添剤を含有するトナー；
　７）少なくとも樹脂、及び染料を含有する樹脂組成物の粉体であって、
　該樹脂のＳＰ値が９．５以上である、粉体；
　８）少なくとも樹脂、染料、ワックス、荷電制御剤および外添剤を含有するトナーであって、
　該樹脂のＳＰ値が９．５以上であるトナー；
　９）少なくとも樹脂、および染料を混合して樹脂－染料混合物を得る工程と、
　前記樹脂－染料混合物を溶融混練して樹脂組成物を得る工程と、
　前記樹脂組成物を粉砕する工程と
を含み、
　前記樹脂のＳＰ値が９．５以上である、樹脂組成物の粉体の製造方法；および
　１０）少なくとも樹脂、染料、ワックス、荷電制御剤および外添剤を混合して樹脂－染料混合物を得る工程と、
　前記樹脂－染料混合物を溶融混練して樹脂組成物を得る工程と、
　前記樹脂組成物を粉砕する工程と
を含み、
　前記樹脂のＳＰ値が９．５以上である、トナーの製造方法。 1) A method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye, wherein the SP value of the resin is 9.5 or more;
2) The method for suppressing powder aggregation according to 1) above, wherein the dye is a disperse dye and / or a solvent dye;
3) A powder of a resin composition used in the method for suppressing powder aggregation according to 1) above, wherein the resin composition contains at least a resin and a dye, and the SP value of the resin is 9.5 or more. Powder of;
4) The method for suppressing powder aggregation according to 1) above, wherein the powder of the resin composition containing at least a resin and a dye is a toner further containing at least a wax, a charge control agent, and an external additive;
5) The method for suppressing powder aggregation according to 4) above, wherein the dye is a disperse dye and / or a solvent dye;
6) A toner for use in the method for suppressing powder aggregation described in 5) above, which contains at least a resin, a dye, a wax, a charge control agent, and an external additive;
7) A powder of a resin composition containing at least a resin and a dye,
A powder having an SP value of 9.5 or more;
8) A toner containing at least a resin, a dye, a wax, a charge control agent and an external additive,
A toner having an SP value of 9.5 or more;
9) mixing at least a resin and a dye to obtain a resin-dye mixture;
A step of melt-kneading the resin-dye mixture to obtain a resin composition;
Crushing the resin composition,
A process for producing a resin composition powder wherein the resin has an SP value of 9.5 or higher; and 10) a resin-dye mixture is obtained by mixing at least a resin, a dye, a wax, a charge control agent and an external additive. Process,
A step of melt-kneading the resin-dye mixture to obtain a resin composition;
Crushing the resin composition,
A method for producing a toner, wherein the SP value of the resin is 9.5 or more.
　本発明により、少なくとも樹脂及び染料を含有する樹脂組成物の粉体における、粉体凝集を抑制する方法を提供することができる。 According to the present invention, a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye can be provided.
　本明細書において、樹脂組成物の「粉体」とは、粒子状等の各種の形状を有する粉体の全てを含む意味で使用する。
　また、本明細書においては特に断りのない限り、「％」及び「部」については、実施例等も含めて、いずれも質量基準で記載する。
　また、ＳＰ値の単位は「（ｃａｌ／ｃｍ３）１／２」である。 In the present specification, the “powder” of the resin composition is used to include all powders having various shapes such as particles.
In the present specification, unless otherwise specified, “%” and “part” are described on a mass basis, including examples.
The unit of the SP value is “(cal / cm 3 ) 1/2 ”.
　上記樹脂組成物の粉体は、少なくともＳＰ値が９．５以上の樹脂を含有する。該樹脂組成物の粉体は、ＳＰ値が９．５以上の樹脂のみを含有することも、ＳＰ値が９．５以上の樹脂と、それ以外の樹脂とを併用することもできる。ＳＰ値が９．５以上の樹脂としては、特に制限されないが、ポリエステルが好ましい。
　上記「それ以外の樹脂」としては特に制限は無く、染料と混合することが可能なものであれば、公知の樹脂の中から使用目的に応じて適宜選択することができる。
　その具体例としては、例えば、スチレン又はスチレン誘導体の重合体、スチレン系共重合体、ポリメチルメタクリレート、ポリブチルメタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エポキシ樹脂、エポキシポリオール樹脂、ポリウレタン、ポリアミド、ポリビニルブチラール、ポリアクリル酸樹脂、ロジン、変性ロジン、テルペン樹脂、脂肪族炭化水素樹脂、脂環族炭化水素樹脂、芳香族系石油樹脂、塩素化パラフィン、パラフィンワックス等が挙げられる。これらの中では、スチレン系共重合体が好ましい。
　上記した樹脂は、いずれも単独で使用してもよいし、２種類以上を併用してもよい。２種類以上の樹脂を併用するときは、ポリエステル樹脂同士を併用するのが好ましい。
　これらの樹脂を単独で、又は併用して用いるとき、樹脂のＳＰ値は通常９．５以上、好ましくは９．５～１５．０、より好ましくは９．５～１２．０、さらに好ましくは９．５～１１．０、特に好ましくは９．８～１０．４である。 The powder of the resin composition contains at least a resin having an SP value of 9.5 or more. The powder of the resin composition may contain only a resin having an SP value of 9.5 or higher, or a resin having an SP value of 9.5 or higher and other resins may be used in combination. Although it does not restrict | limit especially as resin with SP value 9.5 or more, Polyester is preferable.
There is no restriction | limiting in particular as said "other resin", If it can mix with dye, it can select suitably according to a use purpose from well-known resin.
Specific examples thereof include, for example, a polymer of styrene or a styrene derivative, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane. , Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. In these, a styrene-type copolymer is preferable.
Any of the above-described resins may be used alone or in combination of two or more. When two or more kinds of resins are used in combination, it is preferable to use polyester resins together.
When these resins are used alone or in combination, the SP value of the resin is usually 9.5 or more, preferably 9.5 to 15.0, more preferably 9.5 to 12.0, and even more preferably 9 0.5 to 11.0, particularly preferably 9.8 to 10.4.
　上記スチレン又はスチレン誘導体の重合体としては、例えば、ポリスチレン、ポリｐ－クロロスチレン、ポリビニルトルエン等が挙げられる。
　上記スチレン系共重合体としては、例えば、スチレン－ｐ－クロロスチレン共重合体、スチレン－プロピレン共重合体、スチレン－ビニルトルエン共重合体、スチレン－ビニルナフタリン共重合体、スチレン－アクリル酸エステル共重合体（スチレン－アクリル酸メチル共重合体、スチレン－アクリル酸エチル共重合体、スチレン－アクリル酸ブチル共重合体、スチレン－アクリル酸オクチル共重合体等）、スチレン－メタクリル酸エステル共重合体（スチレン－メタクリル酸メチル共重合体、スチレン－メタクリル酸エチル共重合体、スチレン－メタクリル酸ブチル共重合体等）、スチレン－α－クロルメタクリル酸メチル共重合体、スチレン－アクリロニトリル共重合体、スチレン－ビニルメチルケトン共重合体、スチレン－ブタジエン共重合体、スチレン－イソプレン共重合体、スチレン－アクリロニトリル－インデン共重合体、スチレン－マレイン酸共重合体、スチレン－マレイン酸エステル共重合体等が挙げられる。
　これらの樹脂は合成することもできるし、市販品として入手することもできる。 Examples of the styrene or styrene derivative polymer include polystyrene, poly p-chlorostyrene, and polyvinyltoluene.
Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-acrylic acid ester copolymer. Polymers (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer ( Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, etc.), styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ketone copolymer, styrene-butadiene Polymers, styrene - isoprene copolymer, styrene - acrylonitrile - indene copolymer, styrene - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.
These resins can be synthesized or can be obtained as commercial products.
　上記樹脂の市販品の一例としては、ポリエステルとして知られる三菱レーヨン株式会社製のダイヤクロン　ＦＣ－６８４、ダイヤクロン　ＦＣ－２２３２、ダイヤクロン　ＦＣ－１２２４、ダイヤクロン　ＦＣ－３１６、ダイヤクロン　ＥＲ－５０８等；スチレン－アクリル酸エステル共重合体として知られる三井化学株式会社製のＣＰＲ－１００、ＣＰＲ－２５０、ＣＰＲ－３９０等；等が挙げられる。 Examples of commercially available products of the above resins include Diacron FC-684, Diacron FC-2232, Diacron FC-1224, Diacron FC-316, Diacron ER-508, etc. manufactured by Mitsubishi Rayon Co., Ltd., known as polyester. And CPR-100, CPR-250, and CPR-390 manufactured by Mitsui Chemicals, Inc., which are known as styrene-acrylic acid ester copolymers.
　本明細書において、ＳＰ値とは、「Ｋ．　Ｗ．　Ｓｕｈ，　Ｊ．　Ｍ．　Ｃｏｒｂｅｔｔ，　Ｊ．Ａｐｐｌ．　Ｐｏｌｙｍ．　Ｓｃｉ．，　Ｖｏｌ．　１２，　ｐ．２３５９－２３７０（１９６８）．」に開示された、濁点滴定法の結果より求めた値を意味する。この方法は、樹脂０．５ｇをＴ　ｍｌのＴＨＦ（テトラヒドロフラン）に溶解させた溶液に、ＳＰ値の低い貧溶媒（ｎ－ヘキサン）とＳＰ値の高い貧溶媒（脱イオン水）をそれぞれ用いて滴下し、濁りを生じるまでに要した貧溶媒の滴下量をそれぞれ測定する。測定より得られた、ｎ－ヘキサン及び脱イオン水の滴下量から、下記の計算式によりＳＰ値を算出することができる。 In this specification, the SP value is disclosed in “K.W. Suh, J.M. Corbett, J.Appl.Poly.Sci., Vol.12, p.2359-2370 (1968)”. The value obtained from the result of the cloud point titration method. This method uses a poor solvent (n-hexane) with a low SP value and a poor solvent (deionized water) with a high SP value in a solution of 0.5 g of resin dissolved in T ml of THF (tetrahydrofuran). The amount of dripping of the poor solvent required until dropping and turbidity are measured. From the drop amounts of n-hexane and deionized water obtained from the measurement, the SP value can be calculated by the following formula.
ＳＰ値＝（ＶＨ ０．５δｍｌ＋ＶＤ ０．５δｍｈ）／（ＶＨ ０．５＋ＶＤ ０．５）。
　ここで、上記計算式中の各記号等の意味は、以下の通りである。
ＶＨ＝Ｈ／（Ｔ＋Ｈ）。
ＶＤ＝Ｄ／（Ｔ＋Ｄ）。
δｍｌ＝δＴ×Ｔ／（Ｔ＋Ｈ）＋δＨ×Ｈ／（Ｔ＋Ｈ）。
δｍｈ＝δＴ×Ｔ／（Ｔ＋Ｄ）＋δＤ×Ｄ／（Ｔ＋Ｄ）。
ＶＨ：ｎ－ヘキサンの体積分率。
ＶＤ：脱イオン水の体積分率
δｍｌ：ｎ－ヘキサン／ＴＨＦ混合溶液のＳＰ値。
δｍｈ：脱イオン水／ＴＨＦ混合溶液のＳＰ値。
δＴ：ＴＨＦのＳＰ値＝９．５２。
δＨ：ｎ－ヘキサンのＳＰ値＝７．２４。
δＤ：脱イオン水のＳＰ値＝２３．４３。
Ｔ：樹脂を溶解させるのに要したＴＨＦの量（ｍｌ）。
Ｈ：ｎ－ヘキサンの滴下量（ｍｌ）。
Ｄ：脱イオン水の滴下量（ｍｌ）。 SP value = (V H 0.5 δ ml + V D 0.5 δ mh) / (V H 0.5 + V D 0.5).
Here, the meaning of each symbol etc. in the said calculation formula is as follows.
V H = H / (T + H).
V D = D / (T + D).
δ ml = δ T × T / (T + H) + δ H × H / (T + H).
[delta] mh = [delta] T * T / (T + D) + [delta] D * D / (T + D).
V H : Volume fraction of n-hexane.
V D : Volume fraction of deionized water δ ml : SP value of n-hexane / THF mixed solution.
δ mh : SP value of deionized water / THF mixed solution.
δ T : SP value of THF = 9.52.
δ H : SP value of n-hexane = 7.24.
[delta] D: SP value of deionized water = 23.43.
T: The amount of THF required to dissolve the resin (ml).
H: Drip amount of n-hexane (ml).
D: Drip amount of deionized water (ml).
　上記の樹脂組成物の粉体が少なくとも含有する染料としては特に制限は無く、例えば、反応染料、直接染料、酸性染料、金属錯塩酸性染料又は媒染染料等の水溶性染料；及び、分散染料、塩基性染料、建染染料、溶剤染料等の油溶性染料等の非水溶性染料；等が挙げられる。これらの中では非水溶性染料が好ましく、中でも分散染料及び／又は溶剤染料がより好ましい。
　なお、本明細書において「非水溶性染料」とは、水に対して不溶性又は難溶性の染料を意味する。水に対して「難溶性」とは、２５℃の水に対する溶解度が通常０．１１ｇ／リットル以下、好ましくは０．０１ｇ／リットル以下、より好ましくは０．００１ｇ／リットル以下の染料を意味する。 The dye contained in the powder of the above resin composition is not particularly limited, and includes, for example, water-soluble dyes such as reactive dyes, direct dyes, acid dyes, metal complex hydrochloric acid dyes or mordant dyes; and disperse dyes and bases. Water-insoluble dyes such as oil-soluble dyes such as water-soluble dyes, vat dyes, and solvent dyes. Among these, water-insoluble dyes are preferable, and disperse dyes and / or solvent dyes are more preferable.
In the present specification, the “water-insoluble dye” means a dye that is insoluble or hardly soluble in water. “Slightly soluble” in water means a dye having a solubility in water at 25 ° C. of usually 0.11 g / liter or less, preferably 0.01 g / liter or less, more preferably 0.001 g / liter or less.
　反応染料の具体例としては、例えばＣ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｙｅｌｌｏｗ　２、３、１８、８１、８４、８５、９５、９９、１０２等のイエロー染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｏｒａｎｇｅ　５、９、１２、１３、３５、４５、９９等のオレンジ染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｂｒｏｗｎ　２、８、９、１７、３３等のブラウン染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｒｅｄ　３、３：１、４、１３、２４、２９、３１、３３、１２５、１５１、２０６、２１８、２２６、２４５等のレッド染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｖｉｏｌｅｔ　１、２４等のバイオレット染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｂｌｕｅ　２、５、１０、１３、１４、１５、１５：１、４９、６３、７１、７２、７５、１６２、１７６等のブルー染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｇｒｅｅｎ　５、８、１９等のグリーン染料；Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ　Ｂｌａｃｋ　１、８、２３、３９等のブラック染料；等が挙げられる。 Specific examples of reactive dyes include C.I. I. Yellow dyes such as Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102; I. Orange dyes such as Reactive Orange 5, 9, 12, 13, 35, 45, 99; I. Brown dyes such as Reactive Brown 2, 8, 9, 17, 33; I. Red dyes such as Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245; I. Violet dyes such as Reactive Violet 1, 24; I. Blue dyes such as Reactive Blue 2, 5, 10, 13, 14, 15, 15: 1, 49, 63, 71, 72, 75, 162, 176; I. Green dyes such as Reactive Green 5, 8, 19; I. And black dyes such as Reactive Black 1, 8, 23, 39; and the like.
　直接染料の具体例としては、例えばＣ．Ｉ．Ｄｉｒｅｃｔ　Ｙｅｌｌｏｗ　４、５、１１、１２、５０、８６、８７、１２７、１３０、１３２、１４２、１４７、１５３等のイエロー染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｏｒａｎｇｅ　１５、３４、３９、１０２等のオレンジ染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｂｒｏｗｎ　１９５、２０９、２１０等のブラウン染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｒｅｄ　８１、８９、２２４、２２５、２２６、２２７、２３９、２４３、２５２、２５５等のレッド染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｖｉｏｌｅｔ　９、５１、６６等のバイオレット染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｂｌｕｅ　８６、８７、１０８、１９９、２００、２０２、２１８、２３７、２４８、２６７、２７３、２７９、２８１等のブルー染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｇｒｅｅｎ　５９、８０等のグリーン染料；Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｂｌａｃｋ　１９、２２、１１２、１１７、１６１、１７０、１７１等のブラック染料；等が挙げられる。 Specific examples of direct dyes include C.I. I. Yellow dyes such as Direct Yellow 4, 5, 11, 12, 50, 86, 87, 127, 130, 132, 142, 147, 153; I. Orange dyes such as Direct Orange 15, 34, 39, 102; I. Brown dyes such as Direct Brown 195, 209, 210; I. Red dyes such as Direct Red 81, 89, 224, 225, 226, 227, 239, 243, 252, 255; I. Violet dyes such as Direct Violet 9, 51, 66; I. Blue Blue such as Direct Blue 86, 87, 108, 199, 200, 202, 218, 237, 248, 267, 273, 279, 281; I. Direct Green 59, 80 and other green dyes; C.I. I. Direct Black 19, 22, 112, 117, 161, 170, 171 and the like; and the like.
　酸性染料の具体例としては、例えばＣ．Ｉ．Ａｃｉｄ　Ｙｅｌｌｏｗ　１、３、１１、１７、１８、１９、２３、２５、３６、３８、４０、４０：１、４２、４４、４９、５９、５９：１、６１、６５、７２、７３、７９、９９、１０４、１１０、１５９、１６９、１７６、１８４、１９３、２００、２０４、２０７、２１５、２１９、２１９：１、２２０、２３０、２３２、２３５、２４１、２４２、２４６等のイエロー染料；Ｃ．Ｉ．　Ａｃｉｄ　Ｏｒａｎｇｅ　３、７、８、１０、１９、２４、５１、５６、６７、７４、８０、８６、８７、８８、８９、９４、９５、１０７、１０８、１１６、１２２、１２７、１４０、１４２、１４４、１４９、１５２、１５６、１６２、１６６、１６８等のオレンジ染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｒｏｗｎ　２、４、１３、１４、１９、２８、４４、１２３、２２４、２２６、２２７、２４８、２８２、２８３、２８９、２９４、２９７、２９８、３０１、３５５、３５７、４１３等のブラウン染料；Ｃ．Ｉ．Ａｃｉｄ　Ｒｅｄ　１、６、８、９、１３、１８、２７、３５、３７、５２、５４、５７、７３、８２、８８、９７、９７：１、１０６、１１１、１１４、１１８、１１９、１２７、１３１、１３８、１４３、１４５、１５１、１８３、１９５、１９８、２１１、２１５、２１７、２２５、２２６、２４９、２５１、２５４、２５６、２５７、２６０、２６１、２６５、２６６、２７４、２７６、２７７、２８９、２９６、２９９、３１５、３１８、３３６、３３７、３５７、３５９、３６１、３６２、３６４、３６６、３９９、４０７、４１５等のレッド染料；Ｃ．Ｉ．Ａｃｉｄ　Ｖｉｏｌｅｔ　１７、１９、２１、４２、４３、４７、４８、４９、５４、６６、７８、９０、９７、１０２、１０９、１２６等のバイオレット染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｌｕｅ　１、７、９、１５、２３、２５、４０、６１：１、６２、７２、７４、８０、８３、９０、９２、１０３、１０４、１１２、１１３、１１４、１２０、１２７、１２７：１、１２８、１２９、１３８、１４０、１４２、１５６、１５８、１７１、１８２、１８５、１９３、１９９、２０１、２０３、２０４、２０５、２０７、２０９、２２０、２２１、２２４、２２５、２２９、２３０、２３９、２４９、２５８、２６０、２６４、２７７：１、２７８、２７９、２８０、２８４、２９０、２９６、２９８、３００、３１７、３２４、３３３、３３５、３３８、３４２、３５０等のブルー染料；Ｃ．Ｉ．Ａｃｉｄ　Ｇｒｅｅｎ　９、１２、１６、１９、２０、２５、２７、２８、４０、４３、５６、７３、８１、８４、１０４、１０８、１０９等のグリーン染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　１、２、３、２４、２４：１、２６、３１、５０、５２、５２：１、５８、６０、６３、１０７、１０９、１１２、１１９、１３２、１４０、１５５、１７２、１８７、１８８、１９４、２０７、２２２等のブラック染料；等が挙げられる。 Specific examples of acid dyes include C.I. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 72, 73, 79, Yellow dyes such as 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246; I. Acid Orange 3, 7, 8, 10, 19, 24, 51, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, Orange dyes such as 144, 149, 152, 156, 162, 166, 168; I. Brown dyes such as Acid Brown 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413; C. I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, Red dyes such as 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415; I. Violet dyes such as Acid Violet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126; I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, Blue dyes such as 239, 249, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350; I. Acid Green 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109, etc .; I. Acid Black 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 107, 109, 112, 119, 132, 140, 155, 172, 187, Black dyes such as 188, 194, 207, and 222;
　金属錯塩酸性染料の具体例としては、例えばＣ．Ｉ．Ａｃｉｄ　Ｙｅｌｌｏｗ　５９、１１１、１１２、１１６、１６１等のイエロー染料；Ｃ．Ｉ．Ａｃｉｄ　Ｏｒａｎｇｅ　８２、８７、８８、９５、１２２、１４７等のオレンジ染料；Ｃ．Ｉ．Ａｃｉｄ　Ｒｅｄ　２０９、２１１、２１５、２１６、２１７、２５６、２６２、３１７、３５５等のレッド染料；、Ｃ．Ｉ．Ａｃｉｄ　Ｖｉｏｌｅｔ　６６、７５、１１６等のバイオレット染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｌｕｅ　１６７、１６８、１７１、２３４、２５０、２７６等のブルー染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｒｏｗｎ　３０、４４、４５、４６、２２４、２８２、２８３、２９４、２９５、２９６、２９７、３３３、３５２、３５３、３６９、３６８等のブラウン染料；Ｃ．Ｉ．Ａｃｉｄ　Ｇｒｅｅｎ　４３、６０、７６、７７、８０等のグリーン染料；Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　５２：１、１０７、１１０、１３２、１５５、１７９等のブラック染料；等を挙げることができる。 Specific examples of metal complex hydrochloric acid dyes include C.I. I. Acid Yellow 59, 111, 112, 116, 161 etc. yellow dyes; C.I. I. Acid Orange 82, 87, 88, 95, 122, 147 and other orange dyes; C.I. I. Acid Red 209, 211, 215, 216, 217, 256, 262, 317, 355 and other red dyes; I. Violet dyes such as Acid Violet 66, 75, 116; I. Acid Blue 167, 168, 171, 234, 250, 276 and other blue dyes; I. Brown dyes such as Acid Brown 30, 44, 45, 46, 224, 282, 283, 294, 295, 296, 297, 333, 352, 353, 369, 368; I. Acid Green 43, 60, 76, 77, 80, etc. green dyes; C.I. I. A black dye such as Acid Black 52: 1, 107, 110, 132, 155, 179;
　媒染染料の具体例としては、例えばＣ．Ｉ．Ｍｏｒｄａｎｔ　Ｙｅｌｌｏｗ　５、８、１０、１６、２０、２６、３０、３１、３３、４２、４３、４５、５０、５６、６１、６２、６５等のイエロー染料；Ｃ．Ｉ．Ｍｏｒｄａｎｔ　Ｏｒａｎｇｅ　３、４、５、８、１２、１３、１４、２０、２１、２３、２４、２８、２９、３２、３４、３５、３６、３７、４２、４３、４７、４８等のオレンジ染料；Ｃ．Ｉ．Ｍｏｒｄａｎｔ　Ｒｅｄ　１、２、３、４、９、１１、１２、１４、１７、１８、１９、２２、２３、２４、２５、２６、３０、３２、３３、３６、３７、３８、３９、４１、４３、４５、４６、４８、５３、５６、６３、７１、７４、８５、８６、８８、９０、９４、９５等のレッド染料；Ｃ．Ｉ．Ｍｏｒｄａｎｔ　Ｖｉｏｌｅｔ　２、４、５、７、１４、２２、２４、３０、３１、３２、３７、４０、４１、４４、４５、４７、４８、５３、５８等のバイオレット染料；Ｃ．Ｉ．Ｍｏｒｄａｎｔ　Ｂｌｕｅ　２、３、７、８、９、１２、１３、１５、１６、１９、２０、２１、２２、２３、２４、２６、３０、３１、３２、３９、４０、４１、４３、４４、４８、４９、５３、６１、７４、７７、８３、８４等のブルー染料；Ｃ．Ｉ．Ｍｏｒｄａｎｔ　Ｇｒｅｅｎ　１、３、４、５、１０、１５、１９、２６、２９、３３、３４、３５、４１、４３、５３等のグリーン染料；等が挙げられる。 Specific examples of mordant dyes include C.I. I. Yellow Yellow, such as Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 50, 56, 61, 62, 65; I. Orange dyes such as Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, Red dyes such as 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; I. Violet dyes such as Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; I. Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, Blue dyes such as 48, 49, 53, 61, 74, 77, 83, 84; I. Green Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc .;
　塩基性染料の具体例としては、例えばＣ．Ｉ．Ｂａｓｉｃ　Ｙｅｌｌｏｗ　１、２、１１、２８、５１、５７、８７等のイエロー染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｏｒａｎｇｅ　２、１４、２１、２４、３１等のオレンジ染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｂｒｏｗｎ　１、１６、１７等のブラウン染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｒｅｄ　１、２、５、９、１２、１３、１４、１５、１８、２２、２７、２９、３５、３６、４０、５１、７６、１１８等のレッド染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｖｉｏｌｅｔ　１、２、３、４、７、１０、１４、１５、２０、２７等のバイオレット染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｂｌｕｅ　１、３、５、７、９、１６、２２、２４、２５、２６、２８、２９、６４、９９、１１７等のブルー染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｇｒｅｅｎ　１、４、５等のグリーン染料；Ｃ．Ｉ．Ｂａｓｉｃ　Ｂｌａｃｋ　２等のブラック染料；等が挙げられる。 Specific examples of basic dyes include C.I. I. Yellow dyes such as Basic Yellow 1, 2, 11, 28, 51, 57, 87; I. Orange dyes such as Basic Orange 2, 14, 21, 24, 31; I. C. Brown Brown 1, 16, 17, etc. brown dyes; I. Red dyes such as Basic Red 1, 2, 5, 9, 12, 13, 14, 15, 18, 22, 27, 29, 35, 36, 40, 51, 76, 118; I. Violet dyes such as Basic Violet 1, 2, 3, 4, 7, 10, 14, 15, 20, 27; I. Blue dyes such as Basic Blue 1, 3, 5, 7, 9, 16, 22, 24, 25, 26, 28, 29, 64, 99, 117; I. Basic Green 1, 4, 5, etc. green dyes; C.I. I. Black dyes such as Basic Black 2;
　建染染料の具体例としては、例えばＣ．Ｉ．Ｖａｔ　Ｙｅｌｌｏｗ　２、４、１０、２０、３３等のイエロー染料；Ｃ．Ｉ．Ｖａｔ　Ｏｒａｎｇｅ　１、２、３、５、７、９、１３、１５等のオレンジ染料；Ｃ．Ｉ．Ｖａｔ　Ｒｅｄ　１、２、１０、１３、１５、１６、４１、６１等のレッド染料；Ｃ．Ｉ．Ｖａｔ　Ｖｉｏｌｅｔ　１、２、９、１３、２１等のバイオレット染料；Ｃ．Ｉ．Ｖａｔ　Ｂｌｕｅ　１、３、４、５、６、８、１２、１４、１８、１９、２０、２９、３５、４１等のブルー染料；Ｃ．Ｉ．Ｖａｔ　Ｇｒｅｅｎ　１、２、３、４、８、９等のグリーン染料；Ｃ．Ｉ．Ｖａｔ　Ｂｒｏｗｎ　１、３、２５、４４、４６等のブラウン染料；Ｃ．Ｉ．Ｖａｔ　Ｂｌａｃｋ　１、８、９、１３、１４、２０、２５、２７、２９、３６、５６、５７、５９、６０等のブラック染料；等が挙げられる。 Specific examples of vat dyes include C.I. I. Yellow dyes such as Vat Yellow 2, 4, 10, 20, 33; I. Orange dyes such as Vat Orange 1, 2, 3, 5, 7, 9, 13, 15; I. Red dyes such as Vat Red 1, 2, 10, 13, 15, 16, 41, 61; I. Violet dyes such as Vat Violet 1, 2, 9, 13, 21; I. Blue dyes such as Vat Blue 1, 3, 4, 5, 6, 8, 12, 14, 18, 19, 20, 29, 35, 41; I. Green dyes such as Vat Green 1, 2, 3, 4, 8, 9; I. Brown dyes such as Vat Brown 1, 3, 25, 44, 46; I. And black dyes such as Vat Black 1, 8, 9, 13, 14, 20, 25, 27, 29, 36, 56, 57, 59, 60;
　分散染料の具体例としては、例えばＣ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　３、４、５、７、８、９、１３、２３、２４、３０、３３、３４、３９、４２、４４、４９、５０、５１、５４、５６、５８、６０、６３、６４、６６、６８、７１、７４、７６、７９、８２、８３、８５、８６、８８、９０、９１、９３、９８、９９、１００、１０４、１１４、１１６、１１８、１１９、１２２、１２４、１２６、１３５、１４０、１４１、１４９、１６０、１６２、１６３、１６４、１６５、１７９、１８０、１８２、１８３、１８６、１９２、１９８、１９９、２００、２０２、２０４、２１０、２１１、２１５、２１６、２１８、２２４、２３７等のイエロー染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｏｒａｎｇｅ　１、１：１、３、５、７、１１、１３、１７、２０、２１、２３、２５、２５：１、２９、３０、３１、３２、３３、３７、３８、４２、４３、４４、４５、４７、４８、４９、５０、５３、５４、５５、５６、５７、５８、５９、６１、６６、７１、７３、７６、７８、８０、８６、８９、９０、９１、９３、９６、９７、１１８、１１９、１２７、１３０、１３９、１４２等のオレンジ染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　１、４、５、７、１１、１２、１３、１５、１７、２７、４３、４４、５０、５２、５３、５４、５５、５５:１、５６、５８、５９、６０、６５、７０、７２、７３、７４、７５、７６、７８、８１、８２、８６、８８、９０、９１、９２、９３、９６、１０３、１０５、１０６、１０７、１０８、１１０、１１１、１１３、１１７、１１８、１２１、１２２、１２６、１２７、１２８、１３１、１３２、１３４、１３５、１３７、１４３、１４５、１４６、１５１、１５２、１５３、１５４、１５７、１５８、１５９、１６４、１６７、１６９、１７７、１７９、１８１、１８３、１８４、１８５、１８８、１８９、１９０、１９０：１、１９１、１９２、２００、２０１、２０２、２０３、２０５、２０６、２０７、２１０、２２１、２２４、２２５、２２７、２２９、２３９、２４０、２５７、２５８、２７７、２７８、２７９、２８１、２８３、２８８、２９８、３０２、３０３、３１０、３１１、３１２、３２０、３２３、３２４、３２８、３４３、３５９等のレッド染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｖｉｏｌｅｔ　１、４、８、１１、１７、２３、２６、２７、２８、２９、３１、３３、３５、３６、３８、４０、４３、４６、４８、５０、５１、５２、５６、５７、５９、６１、６３、６９、７７，９７等のバイオレット染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｇｒｅｅｎ　９等のグリーン染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｒｏｗｎ　１、２、４、９、１３、１９等のブラウン染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　３、５、７、９、１４、１６、１９、２０、２６、２６：１、２７、３５、４３、４４、５４、５５、５６、５８、６０、６０：１、６２、６４、６４：１、７１、７２、７２：１、７３、７３：１、７５、７７、７９、７９：１、８１、８１：１、８２、８３、８７、９１、９３、９４、９５、６４：１、９６、１０２、１０６、１０８、１１２、１１３、１１５、１１８、１２０、１２２、１２５、１２８、１３０、１３１、１３９、１４１、１４２、１４３、１４５、１４６、１４８、１４９、１５３、１５４、１５８、１６５、１６５：１、１６５：２、１６７、１７１、１７３、１７４、１７６、１８１、１８３、１８５、１８６、１８７、１８９、１９７、１９８、２００、２０１、２０５、２０７、２１１、２１４、２２４、２２５、２５７、２５９、２６６、２６７、２７０、２８１、２８４、２８５、２８７、２８８、２９１、２９３、２９５、２９７、３０１、３１５、３３０、３３３、３３４、３４１、３５３、３５４、３５８、３５９、３６０、３６４、３６５、３６８等のブルー染料；Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌａｃｋ　１、３、１０、２４等のブラック染料が挙げられる。 Specific examples of disperse dyes include C.I. I. Disperse Yellow 3, 4, 5, 7, 8, 9, 13, 23, 24, 30, 33, 34, 39, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 200, 202, 204, 210, 211, 215, 216, 218, Yellow dyes such as 224 and 237; I. Disperse Orange 1, 1: 1, 3, 5, 7, 11, 13, 17, 20, 21, 23, 25, 25: 1, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 86, 89, 90, 91, 93, Orange dyes such as 96, 97, 118, 119, 127, 130, 139, 142; I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 55: 1, 56, 58, 59, 60, 65, 70, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 158, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 190: 1, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 283, 288, 298, 302, 303, 310, 311, 312, 320, 323, Red dyes such as 324, 328, 343, 359; I. Disperse Violet 1, 4, 8, 11, 17, 23, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, Violet dyes such as 59, 61, 63, 69, 77, 97; I. Green dyes such as Disperse Green 9; C.I. I. Disperse Brown 1, 2, 4, 9, 13, 19 etc. brown dyes; I. Disperse Blue 3, 5, 7, 9, 14, 16, 19, 20, 26, 26: 1, 27, 35, 43, 44, 54, 55, 56, 58, 60, 60: 1, 62, 64, 64: 1, 71, 72, 72: 1, 73, 73: 1, 75, 77, 79, 79: 1, 81, 81: 1, 82, 83, 87, 91, 93, 94, 95, 64: 1, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 131, 139, 141, 142, 143, 145, 146, 148, 149, 153, 154, 158, 165, 165: 1, 165: 2, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 20 211, 214, 224, 225, 257, 259, 266, 267, 270, 281, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 334, 341, 353 354, 358, 359, 360, 364, 365, 368, etc .; I. Black dyes such as Disperse Black 1, 3, 10, 24 and the like can be mentioned.
　溶剤染料の具体例としては、例えばＣ．Ｉ．Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　９、１７、１９、２１、２４、３１、３５、４３、４４、５８、６１、８０、９３、１００、１０２、１０３、１０５、１１２、１１４、１６２、１６３等のイエロー染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｏｒａｎｇｅ　１、６７等のオレンジ染料；Ｃ．Ｉ．Ｓｏｌｖｅｔ　Ｒｅｄ　１、３、８、２３、２４、２５、２７、３０、４９、８１、８２、８３、８４、１００、１０９、１２１、１４６等のレッド染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ　８、２１等のバイオレット染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　２、１１、２５、３６、５５、６３、８３、１０５、１１１等のブルー染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｇｒｅｅｎ　３等のグリーン染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｒｏｗｎ　３等のブラウン染料；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　３、５、７、２２、２７、２９等のブラック染料；等がそれぞれ挙げられる。 Specific examples of solvent dyes include C.I. I. Solvent Yellow 9, 17, 19, 21, 24, 31, 35, 43, 44, 58, 61, 80, 93, 100, 102, 103, 105, 112, 114, 162, 163, etc .; C.I. I. Orange dyes such as Solvent Orange 1, 67; I. Red dyes such as Solve Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, 146; I. Violet dyes such as Solvent Violet 8, 21; I. Blue dyes such as Solvent Blue 2, 11, 25, 36, 55, 63, 83, 105, 111; I. Green dyes such as Solvent Green 3; I. Brown dyes such as Solvent Brown 3; C.I. I. And Black dyes such as Solvent Black 3, 5, 7, 22, 27, 29;
　上記の染料は、いずれも単独で使用することができる。また、望みの色調を得る目的等により、２種類以上を併用することもできる。
　例えば、ブラックインクの調製においては、ブルー染料を主体にオレンジ染料、及びレッド染料を適宜配合してブラック色に調色し、これをブラック染料として用いることができる。また、例えばブルー、オレンジ、レッド、バイオレット、又はブラック等の色調を、望みの色調に微調製する目的等により、複数の染料を配合することもできる。 Any of the above dyes can be used alone. Further, two or more kinds can be used in combination for the purpose of obtaining a desired color tone.
For example, in the preparation of a black ink, a blue dye as a main component, an orange dye and a red dye can be appropriately blended to adjust a black color, and this can be used as a black dye. For example, a plurality of dyes can be blended depending on the purpose of finely adjusting the color tone such as blue, orange, red, violet, or black to a desired color tone.
　上記染料のうち、分散染料や溶剤染料を含有する樹脂組成物の粉体は、粉体凝集を生じ易い。また、分散染料や溶剤染料の中でも、昇華性を有する染料は、さらに粉体凝集を生じ易い。本発明の粉体凝集の抑制効果は、これらの染料を含有する樹脂組成物の粉体において、極めて良好に発揮される。 Among the above dyes, the powder of the resin composition containing a disperse dye or a solvent dye tends to cause powder aggregation. Among disperse dyes and solvent dyes, dyes having sublimation properties are more likely to cause powder aggregation. The effect of suppressing the aggregation of the powder of the present invention is exhibited extremely well in the powder of the resin composition containing these dyes.
　本明細書において、昇華性を有する染料とは、「乾熱処理に対する染色堅ろう度試験方法［ＪＩＳ　Ｌ　０８７９：２００５］（２０１０年　確認、平成１７年１月２０日　改定、　財団法人日本規格協会　発行）」における、感熱処理試験（Ｃ法）汚染（ポリエステル）の試験結果が、通常４級以下、好ましくは３．５級又は３級に近い４級以下、より好ましくは３級以下の染料を意味する。すなわち、本明細書においては、感熱処理試験（Ｃ法）汚染（ポリエステル）の試験結果が４級の染料は、昇華転写適性のある染料に含まれる。
　そのような染料のうち、公知の染料としては、例えば以下の染料が挙げられる。
　イエロー染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　３、７、８、２３、３９、５１、５４、６０、７１、８６；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　４３、１１４、１６３；等が挙げられる。
　オレンジ染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｏｒａｎｇｅ　１、１：１、５、２０、２５、２５：１、３３、５６、７６；等が挙げられる。
　ブラウン染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｒｏｗｎ　２；等が挙げられる。
　レッド染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　１１、５０、５３、５５、５５：１、５９、６０、６５、７０、７５、９３、１４６、１５８、１９０、１９０：１、２０７、２３９、２４０；Ｃ．Ｉ．Ｖａｔ　Ｒｅｄ　４１；等が挙げられる。
　バイオレット染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｖｉｏｌｅｔ　８、１７、２３、２７、２８、２９、３６、５７；等が挙げられる。
　ブルー染料としては、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　１９、２６、２６：１、３５、５５、５６、５８、６４、６４：１、７２、７２：１、８１、８１：１、９１、９５、１０８、１３１、１４１、１４５、３５９、３６０；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　３、６３、８３、１０５、１１１；等が挙げられる。 In the present specification, a dye having sublimation property means “a dyeing fastness test method for dry heat treatment [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by the Japanese Standards Association). ”Indicates a dye having a heat treatment test (Method C) contamination (polyester) of a quaternary grade or lower, preferably a quaternary grade close to 3.5 or a tertiary grade, more preferably a tertiary grade or less. . That is, in the present specification, the dye having a quaternary test result of the heat-sensitive test (Method C) contamination (polyester) is included in the dye suitable for sublimation transfer.
Among such dyes, examples of known dyes include the following dyes.
Examples of yellow dyes include C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; I. Solvent Yellow 43, 114, 163; and the like.
Examples of orange dyes include C.I. I. Disperse Orange 1, 1: 1, 5, 20, 25, 25: 1, 33, 56, 76; and the like.
Examples of the brown dye include C.I. I. Disperse Brown 2; etc.
Examples of red dyes include C.I. I. Disperse Red 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240; I. Vat Red 41; and the like.
Examples of the violet dye include C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57;
Examples of blue dyes include C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360; I. Solvent Blue 3, 63, 83, 105, 111; and the like.
　上記樹脂組成物の粉体が含有する染料の総含有量は特に制限はなく、目的に応じて適宜選択することができる。その目安としては、該粉体の総質量に対して通常１～４０％、好ましくは２～３５％、より好ましくは３～２５％である。
　染料の総含有量が１％未満であると着色材料として十分な性能が発揮できず、４０％を超えると該粉体中での染料の溶融又は分散不良が生じ、粉体凝集の抑制が困難になる。 There is no restriction | limiting in particular in the total content of the dye which the powder of the said resin composition contains, According to the objective, it can select suitably. The standard is usually 1 to 40%, preferably 2 to 35%, more preferably 3 to 25% with respect to the total mass of the powder.
When the total content of the dye is less than 1%, sufficient performance as a coloring material cannot be exhibited, and when it exceeds 40%, the dye is not melted or dispersed in the powder, and it is difficult to suppress powder aggregation. become.
　上記樹脂組成物の粉体の用途としては特に制限は無く、例えば紫外線硬化型インキ、熱硬化型インキ、インクジェットインキ、グラビアインキ、オフセットインキ等の印刷インクや液体トナーが含有する着色材料；転写式ハロゲン化銀感光材料；感熱転写方式の記録材料；記録ペン、光記録媒体材料、接着剤等が含有する着色材料；粉体塗料、粉体トナー等が含有する着色材料；等の用途が挙げられる。これらの用途の中では、紫外線硬化型インキ、熱硬化型インキ、インクジェットインキ、グラビアインキ、オフセットインキ等の印刷インクや液体トナー；粉体塗料、粉体トナー；等が含有する、各着色材料としての用途が好ましく、液体トナーに含まれる粉体の着色樹脂組成物、粉体塗料、粉体トナー等が挙げられる。 The use of the resin composition powder is not particularly limited. For example, a coloring material contained in a printing ink or liquid toner such as an ultraviolet curable ink, a thermosetting ink, an inkjet ink, a gravure ink, or an offset ink; Examples include silver halide photosensitive materials; thermal transfer recording materials; coloring materials containing recording pens, optical recording medium materials, adhesives, etc .; coloring materials containing powder paints, powder toners, etc. . Among these uses, as coloring materials contained in printing inks and liquid toners such as ultraviolet curable inks, thermosetting inks, inkjet inks, gravure inks and offset inks; powder paints, powder toners, etc. Are preferable, and examples thereof include powdered colored resin compositions, powder paints, and powder toners contained in liquid toners.
　上記樹脂組成物の粉体は、上記の通り各種の用途に使用することができる。このため、該樹脂組成物の粉体は、その使用用途に応じて樹脂以外の添加剤を含有してもよい。
　添加剤の一例として粉体トナーを挙げると、例えばワックス、荷電制御剤、外添剤等の添加剤が挙げられる。これらの種類、樹脂組成物の粉体の総質量中における含有量、及び、これらの添加剤を含有する粉体トナーの製造方法等については、いずれも公知の先行技術文献に記載されている。上記樹脂組成物の粉体を、粉体トナーとして用いるときは、公知の先行技術文献に基づき粉体トナーとして調製すればよく、他の用途に使用するときも、同様に調製すればよい。
　上記樹脂組成物の粉体は、そのような添加剤を含有するときであっても、十分な凝集抑制効果を発揮する。 The powder of the resin composition can be used for various applications as described above. For this reason, the powder of this resin composition may contain additives other than resin according to the use application.
As an example of the additive, powder toner may be mentioned, for example, additives such as wax, charge control agent, and external additive. These types, the content of the resin composition in the total mass of the powder, and the production method of the powder toner containing these additives are all described in known prior art documents. When the powder of the resin composition is used as a powder toner, it may be prepared as a powder toner based on known prior art documents, and may be prepared in the same manner when used for other purposes.
Even if the powder of the said resin composition contains such an additive, the sufficient aggregation inhibitory effect is exhibited.
　上記の樹脂組成物の粉体の体積平均粒子径（Ｄ５０　Ｖｏｌ．）としては特に制限されず、その使用目的、及び／又は用途により適切な粒子径とすることができる。
　上記の樹脂組成物の粉体を、粉体トナーとして使用するときは通常１μｍ～１２μｍ、好ましくは２μｍ～１０μｍ、より好ましくは３μｍ～１０μｍ、さらに好ましくは５μｍ～８μｍ程度である。
　なお、平均粒子径は、精密粒度分布測定装置（ベックマン・コールター社製、Ｍｕｌｉｔｉｓｉｚｅｒ　４）を用いて測定し、本明細書においては特に断りのない限り、測定値の小数点以下を四捨五入して記載する。 The volume average particle diameter (D50 Vol.) Of the powder of the resin composition is not particularly limited, and may be an appropriate particle diameter depending on the purpose and / or application.
When the powder of the above resin composition is used as a powder toner, it is usually 1 μm to 12 μm, preferably 2 μm to 10 μm, more preferably 3 μm to 10 μm, and further preferably about 5 μm to 8 μm.
The average particle size is measured using a precision particle size distribution analyzer (manufactured by Beckman Coulter, Ltd., Multisizer 4). Unless otherwise specified, the average particle size is rounded off to the nearest decimal point. .
　上記の樹脂組成物の粉体の製造方法としては、少なくとも樹脂と、染料とを混練した後、粉砕、分級を行う粉砕法；昇華性染料等の染料の存在下に、重合性のモノマーを重合させ、同時に形状や大きさを制御しながら粉体を調製する重合法（例えば、乳化重合法、溶解懸濁法、乳化会合法、ポリエステル伸張法等）；等の、公知のいずれの製造方法も使用することができる。樹脂組成物の粉体の製造を高速に行えるという点では粉砕法が好ましく、該粉体の体積平均粒子径を小さくするという点では重合法が好ましい。
　上記のうち、粉砕法による上記の樹脂組成物の粉体の製造は、例えば、下記の製造工程１～３の３つの工程により行うことができる。 As a method for producing the powder of the above resin composition, at least a resin and a dye are kneaded and then pulverized and classified; a polymerizable monomer is polymerized in the presence of a dye such as a sublimation dye And any known production method such as a polymerization method (for example, an emulsion polymerization method, a dissolution suspension method, an emulsion association method, a polyester stretching method, etc.); Can be used. The pulverization method is preferable in that the powder of the resin composition can be produced at high speed, and the polymerization method is preferable in that the volume average particle diameter of the powder is reduced.
Among the above, the production of the resin composition powder by the pulverization method can be performed, for example, by the following three steps of production steps 1 to 3.
［製造工程１］
　少なくともポリエステル樹脂と、昇華性染料とをヘンシェルミキサー等の混合機で混合し、樹脂－染料混合物を得る工程。
［製造工程２］
　製造工程１で得られた樹脂－染料混合物を、密閉式ニーダー；又は、１軸もしくは２軸の押出機；等で溶融混練し、冷却して樹脂組成物を得る工程。
［製造工程３］
　製造工程２で得られた樹脂組成物を、ハンマーミル等で粗粉砕した後、ジェットミル等で微粉砕し、必要に応じて各種分級機やサイクロンを用いて目標とする粒度分布になる様に分級して樹脂組成物の粉体を得る工程。 [Manufacturing process 1]
A step of mixing at least a polyester resin and a sublimation dye with a mixer such as a Henschel mixer to obtain a resin-dye mixture.
[Manufacturing process 2]
A step of melt-kneading the resin-dye mixture obtained in the production step 1 with a closed kneader; or a monoaxial or biaxial extruder; etc., and cooling to obtain a resin composition.
[Manufacturing process 3]
The resin composition obtained in the production process 2 is roughly pulverized with a hammer mill or the like and then finely pulverized with a jet mill or the like so that a desired particle size distribution can be obtained using various classifiers and cyclones as necessary. A step of classification to obtain a resin composition powder.
　本発明の粉体凝集の抑制方法は、特に高温下での輸送時、使用時、又は保存時等において、樹脂組成物の粉体の表面に染料が出てくる現象を抑制することができる。このため、上記樹脂組成物の粉体凝集の抑制が可能となり、耐熱安定性、経時安定性が極めて高い、各種の用途に応用が可能な高品質の樹脂組成物の粉体を提供できる。 The method for suppressing powder aggregation according to the present invention can suppress the phenomenon that the dye appears on the surface of the powder of the resin composition, especially during transportation at high temperature, during use, or during storage. For this reason, it is possible to suppress the powder aggregation of the resin composition, and it is possible to provide a high-quality resin composition powder that has extremely high heat stability and stability over time and can be applied to various applications.
　以下実施例により本発明をさらに詳細に説明するが、これらの実施例により本発明が限定されるものではない。
　実施例中、平均粒子径は、精密粒度分布測定装置「Ｍｕｌｉｔｉｓｉｚｅｒ　４（ベックマン・コールター株式会社製）」を用いて測定した。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
In the examples, the average particle size was measured using a precision particle size distribution measuring apparatus “Multisizer 4 (manufactured by Beckman Coulter, Inc.)”.
［樹脂のＳＰ値の算出］
　ＳＰ値の求め方を、ダイヤクロンＦＣ－３１６を例として以下に記載する。
　ダイヤクロンＦＣ－３１６（０．５ｇ）を１００ｍｌのＴＨＦに溶解して得た溶液を、ｎ－ヘキサンと脱イオン水のそれぞれを用いて濁点まで滴定した。ｎ－ヘキサンおよび脱イオン水の滴定量は、それぞれ３７．１ｍｌおよび１７．３ｍｌであった。
　これらの数値を用い、上記計算式により、ダイヤクロンＦＣ－３１６のＳＰ値を求めた。なお、他の樹脂についても上記と同様にして滴定量を求め、上記計算式により、それぞれのＳＰ値を求めた。結果を下記表１に示す。 [Calculation of SP value of resin]
The method for obtaining the SP value will be described below by taking Diacron FC-316 as an example.
A solution obtained by dissolving Diacron FC-316 (0.5 g) in 100 ml of THF was titrated to the cloud point using each of n-hexane and deionized water. The titration amounts of n-hexane and deionized water were 37.1 ml and 17.3 ml, respectively.
Using these numerical values, the SP value of Diacron FC-316 was determined by the above formula. For other resins, the titration amount was determined in the same manner as described above, and the respective SP values were determined by the above formula. The results are shown in Table 1 below.
　以下に、樹脂組成物の粉体の調製例を記載する。各調製例において用いたミキサーは、象印マホービン株式会社製のＢＭ－ＲＳ０８である。 Hereinafter, preparation examples of the resin composition powder will be described. The mixer used in each preparation example is BM-RS08 manufactured by ZOJIRUSHI CORP.
［実施例１］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６（９１部）、カヤセットイエローA－G（日本化薬株式会社製、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　５４：４．５部）、下記式（１）で表される染料（４．５部）を２００℃に加熱したホットプレート上でメルトブレンドした。冷却後、得られた混練物をミキサーで粉砕することにより、樹脂組成物の粉体を得た。
　なお、下記式（１）で表される染料は、特開平６－１８４４８１号に記載の方法で合成した。 [Example 1]: Preparation of resin composition powder Diacron FC-316 (91 parts) manufactured by Mitsubishi Rayon Co., Ltd., Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow) 54: 4.5 parts), and a dye (4.5 parts) represented by the following formula (1) was melt blended on a hot plate heated to 200 ° C. After cooling, the resulting kneaded product was pulverized with a mixer to obtain a resin composition powder.
The dye represented by the following formula (1) was synthesized by the method described in JP-A-6-184481.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
［実施例２］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６（９０部）、日本化薬株式会社製のＣ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　３５９（６部）、下記式（２）で表される染料（４部）を２００℃に加熱したホットプレート上でメルトブレンドした。冷却後、得られた混練物をジューサーミキサーで粉砕することにより、本発明の樹脂組成物の紛体を得た。
　なお、下記式（２）で表される染料は、特開平６－２２８４４４号に記載の方法で合成した。 [Example 2]: Preparation of resin composition powder Diacron FC-316 (90 parts) manufactured by Mitsubishi Rayon Co., Ltd., C.I. I. Disperse Blue 359 (6 parts) and a dye represented by the following formula (2) (4 parts) were melt blended on a hot plate heated to 200 ° C. After cooling, the resulting kneaded product was pulverized with a juicer mixer to obtain a powder of the resin composition of the present invention.
The dye represented by the following formula (2) was synthesized by the method described in JP-A-6-228444.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
［実施例３］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三菱レイヨン株式会社製のダイヤクロンＦＣ－２２４７を用いる以外は実施例１と同様にして、樹脂組成物の紛体を得た。 [Example 3]: Preparation of resin composition powder The same procedure as in Example 1 was used except that Diacron FC-2247 manufactured by Mitsubishi Rayon Co., Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Thus, a powder of the resin composition was obtained.
［実施例４］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三菱レイヨン株式会社製のダイヤクロンＦＣ－２２４７を用いる以外は実施例２と同様にして、樹脂組成物の紛体を得た。 [Example 4]: Preparation of resin composition powder The same procedure as in Example 2 was used, except that Diacron FC-2247 manufactured by Mitsubishi Rayon Co., Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Thus, a powder of the resin composition was obtained.
［比較例１］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三井化学株式会社製のアルマテックスＣＰＲ－３９０を用いる以外は実施例１と同様にして、比較用の樹脂組成物の紛体を得た。 [Comparative Example 1]: Preparation of Comparative Resin Composition Powder Example 1 except that Almatex CPR-390 manufactured by Mitsui Chemicals, Inc. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. In the same manner, a powder of a comparative resin composition was obtained.
［比較例２］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三井化学株式会社製のアルマテックスＣＰＲ－３９０を用いる以外は実施例２と同様にして、比較用の樹脂組成物の紛体を得た。 [Comparative Example 2]: Preparation of powder of resin composition for comparison Example 2 except that Almatex CPR-390 manufactured by Mitsui Chemicals, Inc. was used in place of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. In the same manner, a powder of a comparative resin composition was obtained.
　上記のようにして調製した各樹脂組成物の粉体のブリード性を、下記方法に基づいて評価した。結果を下記表１に示す。 The bleedability of the powder of each resin composition prepared as described above was evaluated based on the following method. The results are shown in Table 1 below.
［ブリード性試験］
　５０ｍｌのガラス管瓶（日電理化硝子社製、ＳＶ－５０Ａ）に、各実施例及び比較例で調製した樹脂組成物の粉体５．０ｇを秤量し、キャップ蓋をして密閉することにより、試験用の各サンプルを調製した。得られた各サンプルを、下記２条件で保管した後、室温に戻るまで静置した。その後、各樹脂組成物の粉体の電子顕微鏡（日立ハイテクノロジーズ株式会社製、Ｓ－４８００形電界放出形走査電子顕微鏡）写真を撮影し、該粉体からの染料のブリードアウトの有無を、それぞれ下記Ａ～Ｄの評価基準に従って評価した。
条件１：室温（２５℃）下で２４時間保管。
条件２：６０℃±１℃の恒温器に入れ、２４時間保管。 [Bleedability test]
By weighing 5.0 g of the resin composition powder prepared in each example and comparative example into a 50 ml glass tube bottle (manufactured by Nidec Rika Glass Co., Ltd., SV-50A), sealing with a cap lid, Samples for testing were prepared. Each sample obtained was stored under the following two conditions, and then allowed to stand until it returned to room temperature. Thereafter, an electron microscope (S-4800 field emission scanning electron microscope, manufactured by Hitachi High-Technologies Corporation) photograph of the powder of each resin composition was taken, and the presence or absence of bleed out of the dye from the powder was determined. Evaluation was performed according to the following evaluation criteria A to D.
Condition 1: Stored at room temperature (25 ° C.) for 24 hours.
Condition 2: Place in a thermostat at 60 ° C. ± 1 ° C. and store for 24 hours.
［評価基準]
Ａ：ブリードアウトした染料がほとんど観測されない。
Ｂ：ブリードアウトした染料が僅かに観測されるが、１μｍ未満の小さな固体がほとんどである。
Ｃ：ブリードアウトした染料が観測されるが、１μｍ以上３μｍ未満の中型の固体が多数観測される。
Ｄ：ブリードアウトした染料が非常に多く、３μｍ以上の大きな固体が多数観測される。 [Evaluation criteria]
A: Bleed-out dye is hardly observed.
B: Slight bleed-out dye is observed, but most of the solids are less than 1 μm.
C: Although a bleed-out dye is observed, many medium-sized solids of 1 μm or more and less than 3 μm are observed.
D: There are many dyes that bleed out, and many large solids of 3 μm or more are observed.
　下記表１中の略号等は、以下の意味を表す。
ＤｐＹ５４：Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　５４。
ＤｐＢ３５９：Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　３５９。
ＲＴ：室温。 Abbreviations and the like in Table 1 below represent the following meanings.
DpY54: C.I. I. Disperse Yellow 54.
DpB359: C.I. I. Disperse Blue 359.
RT: room temperature.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記樹脂組成物の粉体の一例として、粉体トナーを調製し、その凝集の抑制効果を試験した。 As an example of the resin composition powder, a powder toner was prepared, and the effect of suppressing the aggregation was tested.
［実施例５］
（工程１）
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６（１００部）、カヤセットイエローＡ－Ｇ（日本化薬株式会社製、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　５４：５部）、上記式（１）で表される染料（５部）、ボントロン　Ｅ－８４（１部）、カルナバワックスＣ１（４部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間予備混合した後、二軸押出機により溶融混練した。得られた溶融混練物を粉砕・分級機を用いて粉砕・分級することにより、平均粒子径が７．８μｍのトナー母粒子を得た。
（工程２）
　調製例１（工程１）で得られたトナー母粒子（１００部）、クラリアントジャパン社製のＨ０５ＴＭ（１．５部）、キャボット社製のＴＧ－８１１Ｆ（１．５部）、チタン工業社製のＳＴＴ－３０Ａ（０．５部）およびＳＷ－３５０（１．０部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間撹拌し、イエロートナーを調製した。 [Example 5]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (100 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5 parts), represented by the above formula (1) Dye (5 parts), Bontron E-84 (1 part) and Carnauba wax C1 (4 parts) were placed in a Henschel mixer, premixed for 10 minutes at a rotational speed of 30 m / sec, and then melt-kneaded by a twin screw extruder. did. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.8 μm.
(Process 2)
Toner base particles (100 parts) obtained in Preparation Example 1 (Step 1), H05TM (1.5 parts) manufactured by Clariant Japan, TG-811F (1.5 parts) manufactured by Cabot, manufactured by Titanium Industry Co., Ltd. STT-30A (0.5 part) and SW-350 (1.0 part) were stirred in a Henschel mixer for 10 minutes at a rotational speed of 30 m / sec to prepare a yellow toner.
［実施例６］
（工程１）
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６（９６部）、Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　３５９（８部）、上記式（２）で表される染料（６部）、ボントロン　Ｅ－８４（１部）、カルナバワックスＣ１（４部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間予備混合した後、二軸押出機により溶融混練した。得られた溶融混練物を粉砕・分級機を用いて粉砕・分級することにより、平均粒子径が７．９μｍのトナー母粒子を得た。
（工程２）
　調製例２（工程１）で得られたトナー母粒子（１００部）、クラリアントジャパン社製のＨ０５ＴＭ（１．５部）、キャボット社製のＴＧ－８１１Ｆ（１．５部）、チタン工業社製のＳＴＴ－３０Ａ（０．５部）およびＳＷ－３５０（１．０部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間撹拌し、シアントナーを調製した。 [Example 6]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (96 parts), C.I. I. Disperse Blue 359 (8 parts), dye represented by the above formula (2) (6 parts), Bontron E-84 (1 part) and carnauba wax C1 (4 parts) were placed in a Henschel mixer and rotated at 30 m / sec. After premixing at a speed for 10 minutes, the mixture was melt-kneaded by a twin screw extruder. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.9 μm.
(Process 2)
Toner base particles (100 parts) obtained in Preparation Example 2 (Step 1), H05TM (1.5 parts) manufactured by Clariant Japan, TG-811F (1.5 parts) manufactured by Cabot, and Titanium Industry Co., Ltd. STT-30A (0.5 part) and SW-350 (1.0 part) were placed in a Henschel mixer and stirred at a rotational speed of 30 m / second for 10 minutes to prepare a cyan toner.
［比較例３］
（工程１）
　三井化学株式会社製のアルマテックスＣＰＲ－３９０（１００部）、カヤセットイエローＡ－Ｇ（日本化薬株式会社製、Ｃ．Ｉ．ディスパースイエロー５４：５部）、上記式（１）で表される染料（５部）ボントロン　Ｅ－８４（１部）、カルナバワックスＣ１（４部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間予備混合した後、二軸押出機により溶融混練した。得られた溶融混練物を粉砕・分級機を用いて粉砕・分級することにより、平均粒子径が７．８μｍのトナー母粒子を得た。
（工程２）
　調製例３（工程１）で得られたトナー母粒子（１００部）、クラリアントジャパン社製のＨ０５ＴＭ（１．５部）、キャボット社製のＴＧ－８１１Ｆ（１．５部）、チタン工業社製のＳＷ－３５０（１．０部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間撹拌し、染料を１種類しか含まない比較用のイエロートナーを得た。 [Comparative Example 3]
(Process 1)
Almatex CPR-390 (100 parts) manufactured by Mitsui Chemicals, Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5 parts), represented by the above formula (1) Dye (5 parts) Bontron E-84 (1 part) and Carnauba wax C1 (4 parts) are placed in a Henschel mixer, premixed for 10 minutes at a rotational speed of 30 m / sec, and then melt-kneaded by a twin screw extruder. did. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.8 μm.
(Process 2)
Toner base particles (100 parts) obtained in Preparation Example 3 (Step 1), H05TM (1.5 parts) manufactured by Clariant Japan, TG-811F (1.5 parts) manufactured by Cabot, manufactured by Titanium Industry Co., Ltd. Of SW-350 (1.0 part) was placed in a Henschel mixer and stirred at a rotational speed of 30 m / sec for 10 minutes to obtain a comparative yellow toner containing only one type of dye.
［比較例４］
（工程１）
　三井化学株式会社製のアルマテックスＣＰＲ－３９０（９６部）、Ｃ．Ｉ．ディスパースブルー３５９（８部）、下記式（２）で表される染料（６部）、ボントロン　Ｅ－８４（１部）、カルナバワックスＣ１（４部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間予備混合した後、二軸押出機により溶融混練した。得られた溶融混練物を粉砕・分級機を用いて粉砕・分級することにより、平均粒子径が７．９μｍのトナー母粒子を得た。
（工程２）
　調製例２（工程１）で得られたトナー母粒子（１００部）、クラリアントジャパン社製のＨ０５ＴＭ（１．５部）、キャボット社製のＴＧ－８１１Ｆ（１．５部）、チタン工業社製のＳＷ－３５０（１．０部）をヘンシェルミキサーに入れ、３０ｍ／秒の回転速度で１０分間撹拌し、シアントナーを調製した。 [Comparative Example 4]
(Process 1)
Almatex CPR-390 (96 parts) manufactured by Mitsui Chemicals, C.I. I. Disperse Blue 359 (8 parts), a dye represented by the following formula (2) (6 parts), Bontron E-84 (1 part), and Carnauba wax C1 (4 parts) were placed in a Henschel mixer, 30 m / sec. After premixing for 10 minutes at a rotational speed, the mixture was melt-kneaded by a twin screw extruder. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain toner base particles having an average particle diameter of 7.9 μm.
(Process 2)
Toner base particles (100 parts) obtained in Preparation Example 2 (Step 1), H05TM (1.5 parts) manufactured by Clariant Japan, TG-811F (1.5 parts) manufactured by Cabot, and Titanium Industry Co., Ltd. Of SW-350 (1.0 part) was placed in a Henschel mixer and stirred at a rotational speed of 30 m / sec for 10 minutes to prepare a cyan toner.
　上記のようにして調製した各トナーのブリード性、凝集性、凝集塊の有無を、下記方法に基づいて評価した。試験結果と、使用した各樹脂のＳＰ値を、下記表２に示す。
　なお、下記表２中の「ＲＴ」は、室温を意味する。 The bleedability, cohesiveness, and presence / absence of aggregates of each toner prepared as described above were evaluated based on the following methods. The test results and the SP value of each resin used are shown in Table 2 below.
In Table 2 below, “RT” means room temperature.
［ブリード性試験］
　５０ｍｌのガラス管瓶（日電理化硝子社製、ＳＶ－５０Ａ）に、各実施例及び比較例で調製した各トナー５．０ｇを秤量し、キャップ蓋をして密閉することにより、試験用の各サンプルを調製した。得られた各サンプルを下記２条件で保管した後、室温に戻るまで静置した。その後、各トナーの電子顕微鏡（日立ハイテクノロジーズ株式会社製、Ｓ－４８００形電界放出形走査電子顕微鏡）写真を撮影し、該粉体からの染料のブリードアウトの有無を、それぞれ下記Ａ～Ｄの評価基準に従って評価した。
条件１：室温（２５℃）下で２４時間保管。
条件２：６０℃±１℃の恒温器に入れ、２４時間保管。 [Bleedability test]
Each toner for testing was weighed in a 50 ml glass tube bottle (manufactured by Nippon Denka Glass Co., Ltd., SV-50A) by weighing 5.0 g of each toner prepared in each example and comparative example, and sealing with a cap lid. Samples were prepared. Each sample obtained was stored under the following two conditions, and then allowed to stand until it returned to room temperature. Thereafter, photographs of each toner were taken with an electron microscope (S-4800 field emission scanning electron microscope, manufactured by Hitachi High-Technologies Corporation), and the presence or absence of bleed out of the dye from the powder was determined according to A to D below. Evaluation was performed according to the evaluation criteria.
Condition 1: Stored at room temperature (25 ° C.) for 24 hours.
Condition 2: Place in a thermostat at 60 ° C. ± 1 ° C. and store for 24 hours.
［評価基準]
Ａ：ブリードアウトした染料がほとんど観測されない。
Ｂ：ブリードアウトした染料が観測されるが、１μｍ未満の小さな固体がほとんどである。
Ｃ：ブリードアウトした染料が観測されるが、１μｍ以上３μｍ未満の中型の固体が多数観測される。
Ｄ：ブリードアウトした染料が非常に多く、３μｍ以上の大きな固体が多数観測される。 [Evaluation criteria]
A: Bleed-out dye is hardly observed.
B: Bleeded dye is observed, but most of the solids are less than 1 μm.
C: Although a bleed-out dye is observed, many medium-sized solids of 1 μm or more and less than 3 μm are observed.
D: There are many dyes that bleed out, and many large solids of 3 μm or more are observed.
［凝集性評価試験］
　５０ｍｌのガラス管瓶（日電理化硝子社製、ＳＶ－５０Ａ）に、各実施例及び比較例で調製した各トナー５．０ｇを秤量し、キャップ蓋をして密閉することにより、試験用の各サンプルを調製した。得られた各サンプルを下記４条件で保管した後、室温に戻るまで静置した。その後、キャップ蓋を開けてガラス管瓶を逆さまにし、各粉体トナーの排出状態、及び粉体の凝集塊の有無を、それぞれ下記Ａ～Ｃの評価基準に従って評価した。
条件１：室温（２５℃）下で２４時間保管。
条件２：４０℃±１℃の恒温器に入れ、２４時間保管。
条件３：５０℃±１℃の恒温器に入れ、２４時間保管。
条件４：６０℃±１℃の恒温器に入れ、２４時間保管。 [Cohesiveness evaluation test]
Each toner for testing was weighed in a 50 ml glass tube bottle (manufactured by Nippon Denka Glass Co., Ltd., SV-50A) by weighing 5.0 g of each toner prepared in each example and comparative example, and sealing with a cap lid. Samples were prepared. Each obtained sample was stored under the following four conditions, and then allowed to stand until it returned to room temperature. Thereafter, the cap lid was opened and the glass tube bottle was turned upside down, and the discharge state of each powder toner and the presence or absence of powder agglomerates were evaluated according to the following evaluation criteria AC.
Condition 1: Stored at room temperature (25 ° C.) for 24 hours.
Condition 2: Place in a thermostat at 40 ° C ± 1 ° C and store for 24 hours.
Condition 3: Place in a thermostat at 50 ° C. ± 1 ° C. and store for 24 hours.
Condition 4: Place in a thermostat at 60 ° C. ± 1 ° C. and store for 24 hours.
［凝集性評価基準］
Ａ：逆さまにした直後にトナーが自然落下により排出される。
Ｂ：逆さまにしてもすぐには排出されないが、３０秒～１分以内にトナーが自然落下して排出される。
Ｃ：逆さまにして１分以上経ってもトナーは自然落下しない。
　粉体が凝集するほど自然落下しにくくなるため、自然落下までの時間が短い方が、粉体凝集が生じていないことを意味し、優れた状態である。 [Aggregation evaluation criteria]
A: Toner is discharged by natural fall immediately after turning upside down.
B: Even if it is turned upside down, it is not immediately discharged, but the toner naturally falls and is discharged within 30 seconds to 1 minute.
C: The toner does not fall spontaneously even if it is upside down for more than 1 minute.
The more the powder is agglomerated, the more difficult it is to spontaneously fall. Therefore, the shorter the time to natural fall means that powder agglomeration does not occur, which is an excellent state.
［凝集塊の有無］
Ａ：自然落下したトナーに凝集塊は見当たらない。
Ｂ：自然落下したトナーは僅かに塊状になっているが、指で押すとすぐに粉状に戻る。
Ｃ：落下したトナーには凝集塊があり、指で押しても粉状には戻らない。
　粉体が凝集塊を生じないほど優れた状態であることを意味する。 [Presence of agglomerates]
A: Agglomerates are not found in the toner that has dropped naturally.
B: Although the toner that has fallen naturally is slightly agglomerated, it immediately returns to powder when pressed with a finger.
C: The dropped toner has agglomerates and does not return to powder when pressed with a finger.
It means that the powder is in such an excellent state that no agglomerates are formed.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１から明らかなように、本発明の樹脂組成物の粉体は、高温下におけるブリードアウトの抑制効果を有することが明らかとなった。また、表２から明らかなように、本発明の粉体トナーは、凝集性及び凝集塊の形成のいずれの面からも粉体凝集が低減されており、粉体凝集の抑制効果を有することが明らかとなった。ブリードアウトの評価結果がＡからＤへと悪化するのに伴い、凝集性及び凝集塊の状態も悪化し、ブリードアウトと凝集性には相関があることが確認された。 As is clear from Table 1, it was revealed that the resin composition powder of the present invention has an effect of suppressing bleed-out at high temperatures. Further, as is apparent from Table 2, the powder toner of the present invention has reduced powder aggregation from both aspects of aggregation and formation of aggregates, and has an effect of suppressing powder aggregation. It became clear. As the bleed-out evaluation result deteriorated from A to D, the cohesiveness and the state of the aggregate also deteriorated, and it was confirmed that there is a correlation between the bleed-out and the cohesiveness.
［実施例７］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＦＣ－２２３２を用いる以外は実施例１と同様にして、樹脂組成物の粉体を得た。 [Example 7]: Preparation of resin composition powder In the same manner as in Example 1 except that FC-2232 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
［実施例８］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＦＣ－２２３２を用いる以外は実施例２と同様にして、樹脂組成物の粉体を得た。 [Example 8]: Preparation of resin composition powder In the same manner as in Example 2 except that FC-2232 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
［実施例９］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＭ－３２５を用いる以外は実施例１と同様にして、樹脂組成物の粉体を得た。 [Example 9]: Preparation of resin composition powder In the same manner as in Example 1 except that M-325 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
［実施例１０］：樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＭ－３２５を用いる以外は実施例２と同様にして、樹脂組成物の粉体を得た。 [Example 10]: Preparation of resin composition powder In the same manner as in Example 2 except that M-325 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. A powder of the resin composition was obtained.
［比較例５］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＳＢ－３９１を用いる以外は実施例１と同様にして、比較用の樹脂組成物の粉体を得た。 [Comparative Example 5]: Preparation of powder of resin composition for comparison Example 1 except that SB-391 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Similarly, a resin composition powder for comparison was obtained.
［比較例６］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＳＢ－３９１を用いる以外は実施例２と同様にして、比較用の樹脂組成物の粉体を得た。 [Comparative Example 6]: Preparation of powder of resin composition for comparison Example 2 except that SB-391 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Similarly, a resin composition powder for comparison was obtained.
［比較例７］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＳＢ－３７０を用いる以外は実施例１と同様にして、比較用の樹脂組成物の粉体を得た。 [Comparative Example 7]: Preparation of powder of resin composition for comparison Example 1 except that SB-370 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Similarly, a resin composition powder for comparison was obtained.
［比較例８］：比較用の樹脂組成物の粉体の調製
　三菱レイヨン株式会社製のダイヤクロンＦＣ－３１６の代わりに、三洋化成工業株式会社製のＳＢ－３７０を用いる以外は実施例２と同様にして、比較用の樹脂組成物の粉体を得た。 [Comparative Example 8]: Preparation of Comparative Resin Composition Powder Example 2 was used except that SB-370 manufactured by Sanyo Chemical Industries, Ltd. was used instead of Diacron FC-316 manufactured by Mitsubishi Rayon Co., Ltd. Similarly, a resin composition powder for comparison was obtained.
　上記のようにして調製した実施例５～８及び比較例３～６の各樹脂組成物の粉体のブリード性を、上記［ブリード性試験］及び［評価基準］と同様にして評価した。結果を下記表３に示す。 The bleedability of the powders of the resin compositions of Examples 5 to 8 and Comparative Examples 3 to 6 prepared as described above was evaluated in the same manner as in the above [bleedability test] and [evaluation criteria]. The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表３の結果から明らかなように、各実施例はブリードアウトの抑制効果、特に高温下でのブリードアウトの抑制効果が優れることが確認された。 As is clear from the results in Table 3, it was confirmed that each example was excellent in the bleed-out suppression effect, particularly the bleed-out suppression effect at high temperatures.
　本発明の粉体凝集の抑制方法は、各種の用途に使用可能な、染料を含有する樹脂組成物の粉体の凝集を抑制できるため極めて有用である。 The method for suppressing powder aggregation of the present invention is extremely useful because it can suppress aggregation of powder of a resin composition containing a dye that can be used in various applications.

Claims (10)

  1. 　少なくとも樹脂、及び染料を含有する樹脂組成物の粉体における、粉体凝集の抑制方法であって、該樹脂のＳＰ値が９．５以上である、粉体凝集の抑制方法。 A method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and a dye, wherein the SP value of the resin is 9.5 or more.
  2. 　上記染料が、分散染料及び／又は溶剤染料である、請求項１に記載の粉体凝集の抑制方法。 The method for suppressing powder aggregation according to claim 1, wherein the dye is a disperse dye and / or a solvent dye.
  3. 　請求項１に記載の粉体凝集の抑制方法に用いる樹脂組成物の粉体であって、少なくとも樹脂、及び染料を含有し、該樹脂のＳＰ値が９．５以上である樹脂組成物の紛体。 A powder of a resin composition for use in the method for suppressing powder aggregation according to claim 1, comprising at least a resin and a dye, wherein the resin has an SP value of 9.5 or more. .
  4. 　少なくとも樹脂、及び染料を含有する樹脂組成物の粉体が、さらにワックス、荷電制御剤、及び外添剤を少なくとも含有するトナーである、請求項１に記載の粉体凝集の抑制方法。 2. The method for suppressing powder aggregation according to claim 1, wherein the powder of the resin composition containing at least a resin and a dye is a toner further containing at least a wax, a charge control agent, and an external additive.
  5. 　上記染料が、分散染料及び／又は溶剤染料である、請求項４に記載の粉体凝集の抑制方法。 The method for suppressing powder aggregation according to claim 4, wherein the dye is a disperse dye and / or a solvent dye.
  6. 　請求項５の粉体凝集の抑制方法に用いるトナーであって、少なくとも樹脂、染料、ワックス、荷電制御剤、及び外添剤を含有するトナー。 6. A toner for use in the powder aggregation suppressing method according to claim 5, wherein the toner contains at least a resin, a dye, a wax, a charge control agent, and an external additive.
  7. 　少なくとも樹脂、及び染料を含有する樹脂組成物の粉体であって、
    　該樹脂のＳＰ値が９．５以上である、粉体。     A powder of a resin composition containing at least a resin and a dye,
    The powder whose SP value of this resin is 9.5 or more.
  8. 　少なくとも樹脂、染料、ワックス、荷電制御剤および外添剤を含有するトナーであって、
    　該樹脂のＳＰ値が９．５以上であるトナー。     A toner containing at least a resin, a dye, a wax, a charge control agent and an external additive,
    A toner having an SP value of 9.5 or more.
  9. 　少なくとも樹脂、および染料を混合して樹脂－染料混合物を得る工程と、
    　前記樹脂－染料混合物を溶融混練して樹脂組成物を得る工程と、
    　前記樹脂組成物を粉砕する工程と
    を含み、
    　前記樹脂のＳＰ値が９．５以上である、樹脂組成物の粉体の製造方法。     Mixing at least a resin and a dye to obtain a resin-dye mixture;
    A step of melt-kneading the resin-dye mixture to obtain a resin composition;
    Crushing the resin composition,
    The manufacturing method of the powder of the resin composition whose SP value of the said resin is 9.5 or more.
  10. 　少なくとも樹脂、染料、ワックス、荷電制御剤および外添剤を混合して樹脂－染料混合物を得る工程と、
    　前記樹脂－染料混合物を溶融混練して樹脂組成物を得る工程と、
    　前記樹脂組成物を粉砕する工程と
    を含み、
    　前記樹脂のＳＰ値が９．５以上である、トナーの製造方法。     Mixing at least a resin, a dye, a wax, a charge control agent and an external additive to obtain a resin-dye mixture;
    A step of melt-kneading the resin-dye mixture to obtain a resin composition;
    Crushing the resin composition,
    A method for producing a toner, wherein the SP value of the resin is 9.5 or more.
PCT/JP2015/068908 2014-07-04 2015-06-30 Method for inhibiting agglomeration of powder WO2016002813A1 (en)

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