JP6249526B2 - Method for suppressing powder aggregation - Google Patents

Description

  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. 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.

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.
As dry powder toners and liquid toners used in the electrophotographic system, for example, various types are disclosed in Patent Documents 2 to 5.
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 JP-A-5-27474 Japanese Patent Laid-Open No. 9-73198 Japanese Patent Laid-Open No. 3-18866 Japanese Patent Laid-Open No. 02-295787 Japanese Patent Application Laid-Open No. 06-051591 Japanese Patent Laid-Open No. 10-058638 JP 2000-029238 A JP 2006-500602 Gazette

  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 two kinds of dyes.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least one of the two types of dyes is contained in the powder of the resin composition containing at least a resin and two types of dyes. The present invention was completed by finding that the above problems can be solved by using a disperse dye or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml. That is, the present invention relates to the following (1) to (4).

(1)
A method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and at least two types of dyes, wherein at least one of the at least two types of dye has a solubility in acetone. A method for suppressing powder aggregation, which is a disperse dye or an oil-soluble dye of 0.01 g / 100 ml to 20 g / 100 ml.
(2)
Among the at least two kinds of dyes, at least one dye is a disperse dye or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml, and at least one dye is a disperse dye or basic dye. The method for suppressing powder aggregation according to claim 1, wherein the method is a dye selected from the group of oil-soluble dyes comprising dyes, vat dyes, and solvent dyes.
(3)
Among the at least two kinds of dyes, at least one dye is a disperse dye or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml, and at least one dye is a disperse dye or basic dye. The method for suppressing powder aggregation according to claim 1, which is a dye selected from the group of oil-soluble dyes consisting of dyes and solvent dyes.
(4)
Of the at least two dyes, at least one dye is a disperse dye or an oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml, and at least one dye is represented by the following formula (1): And the method for suppressing powder aggregation according to claim 1, which is an oil-soluble dye selected from Formula (2).

  According to the present invention, a method of suppressing powder aggregation in a powder of a resin composition containing at least a resin and two kinds of dyes can be provided.

Hereinafter, the present invention will be described in detail. Unless otherwise specified, in this specification, “parts” means parts by mass, and “%” means mass%, including examples.
The present invention relates to "a method for suppressing powder aggregation in a powder of a resin composition containing at least a resin and two types of dyes, wherein at least one type of the two types of dyes is used for acetone. The present invention relates to a method for suppressing powder aggregation, which is a disperse dye or an oil-soluble dye having a solubility of 0.01 g / 100 ml to 20 g / 100 ml. In other words, at least two or more kinds of dyes are added by adding one kind of dye to the above-mentioned problem in the powder of the resin composition containing at least one kind of dye selected from resin and disperse dye or oil-soluble dye. And the above-mentioned problem by containing at least one of the two or more dyes as a disperse dye or an oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml. Is a solution.
The solubility in acetone is preferably 0.02 g / 100 ml to 15 g / 100 ml, more preferably 0.04 g / 100 ml to 10 g / 100 ml.
Further, the “powder” of the resin composition is used in the meaning including all powders having various shapes such as particles.
When the powder of the resin composition contains two kinds of dyes, if one of the dyes is a disperse beverage or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml, the rest The one kind of dye is not particularly limited. The remaining one kind of dye may be the various dyes described below, or a disperse beverage or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml.
When the resin composition powder contains three or more types of dyes, all the dyes may be dispersed beverages or oil-soluble dyes having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml. Of these dyes, only one type may be a disperse beverage or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml. In such a case, among a plurality of types of dyes, more than half of the dyes are preferably a dispersion beverage or oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml, and the solubility in acetone is preferably It is more preferable that there is one kind of dye other than 0.01 g / 100 ml to 20 g / 100 ml of the dispersion beverage or the oil-soluble dye.
When the resin composition contains a dye other than a disperse beverage having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml or an oil-soluble dye, the solubility in acetone is 0.01 g / 100 ml to 20 g / 100 ml. As for the content of the dispersion beverage or oil-soluble dye and the other dyes, the former total content is usually 50 to 80%, preferably 60 to 80%, and the latter total content is usually 20% to 50%. %, Preferably 20% to 30%.

The solubility of the dye in acetone was determined by adding an excessive disperse dye or oil-soluble dye solid in 100 ml of acetone at 25 ° C. and stirring for 1 hour. No. 5C, 70 mm), suction bottle, and aspirator (Azuwan Corporation, ASPIRATOR model number AS-01, ultimate vacuum 0.09 MPa (25 ° C.)) are filtered under reduced pressure, and the mass of the filtration residue is measured. To decide.
The measurement is performed at least twice for one dye, and the value obtained by rounding the second significant digit of the obtained value is taken as the solubility of the dye. When there is a difference between the two measurement values, the numerical values obtained by the two measurements are described as the lower limit value and the upper limit value.
Those skilled in the art can easily measure the solubility in acetone. As an example of such a dye, the three primary colors of yellow, magenta, and cyan are C.I. I. Disperse Yellow 54, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 359 is exemplified as a disperse dye or an oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml.

Of the two types of dyes contained in the powder of the resin composition, the type of dye other than the disperse dye or the oil-soluble dye having a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml is not particularly limited. For example, water-insoluble dyes including water-soluble dyes such as reactive dyes, direct dyes, acid dyes, metal complex hydrochloric acid dyes or acid mordant dyes; and oil-soluble dyes such as disperse dyes, basic dyes, vat dyes and solvent dyes Dyes; and the like. Among these, water-insoluble dyes including oil-soluble dyes such as disperse dyes, basic dyes, and vat dyes are preferable, and water-insoluble dyes including oil-soluble dyes such as disperse dyes and basic 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 0.01 g / liter or less, preferably 0.001 g / liter or less.

  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. Black dyes such as Reactive Black 1, 8, 23, 39; and the like.

Specific examples of the direct dye 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 dyes such as Direct Blue 86, 87, 108, 199, 200, 202, 218, 237, 248, 267, 273, 279, 281; I. Green dyes such as direct green 59 and 80; I. Direct black 19
, 22, 112, 117, 161, 170, 171 and the like;

  Specific examples of the acid dye 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;

  Specific examples of the metal complex hydrochloric acid dye include C.I. I. Acid yellow 59, 111, 112, 116, 161 and the like yellow dyes; C.I. I. Orange dyes such as Acid Orange 82, 87, C.I. Acid Orange 88, C.I. Acid Orange 95, C.I. Acid Orange 122, C.I. Acid Orange 147; I. Red dyes such as Acid Red 209, 211, 215, 216, 217, 256, 262, 317, and 355; I. Violet dyes such as Acid Violet 66, 75 and 116; I. Acid blue 167, 168, 171, 234, 250, 276 and the like; 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 and other green dyes; C.I. I. Acid black 52: 1, 107, 110, 132, 155, 179 and the like black dyes;

  Specific examples of the acid mordant dye include C.I. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 50, 56, 61, 62, 65, etc. yellow dyes; C.I. I. Orange dyes such as mordanto 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. Moldand 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 C., 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; I. Violet dyes such as mold violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; I. Moldan 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, etc .; I. And green dyes such as Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53;

  Specific examples of the basic dye 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. Brown dyes such as Basic Brown 1, 16, 17; 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. B. Blue dyes such as Basic Blue 1, 3, 5, 7, 9, 16, 22, 24, 25, 26, 28, 29, 64, 99, 117; I. Green dyes such as Basic Green 1, 4, 5; I. Black dyes such as Basic Black 2;

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. B. Blue dyes such as 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. Bat Black 1, 8, 9, 13, 14
, 20, 25, 27, 29, 36, 56, 57, 59, 60 and the like; and the like.

  Specific examples of the disperse dye 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, 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 C., 96, 97, 118, 119, 127, 130, 139, 142; I. Disperse thread 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, Red dyes such as 328, 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 C., 59, 61, 63, 69, 77, 97; I. Green dyes such as disperse green 9; I. Brown dyes such as disperse brown 1, 2, 4, 9, 13, 19; 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, Blue dyes such as 358, 359, 360, 364, 365, 368; I. Examples thereof include black dyes such as Disperse Black 1, 3, 10, 24.

  Specific examples of the solvent dye include C.I. I. Yellow dyes such as Solvent Yellow 9, 17, 19, 21, 24, 31, 35, 43, 44, 58, 61, 80, 93, 100, 102, 103, 105, 112, 114, 162, 163; I. Orange dyes such as Solvent Orange 1, 67; I. Red dyes such as Solvent 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, 3, 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, and the like.

Any of the above dyes may be used alone. Further, two or more types may be used (mixed) in accordance with 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. Further, for example, a plurality of dyes may be blended for the purpose of finely adjusting a color tone such as blue, orange, red, violet, or black to a desired color tone.
However, even when a plurality of dyes are used in combination, at least one of the dyes contained in the powder of the resin composition has a solubility in acetone of 0.01 g / 100 ml to 20 g / 100 ml of disperse dye or oil-soluble dye.

  Among the above dyes, there is a difference in the easiness of coming out to the surface of the resin composition, and disperse dyes and oil-soluble dyes are likely to appear on the surface, and as a result, powder aggregation tends to occur. Further, among disperse dyes and oil-soluble dyes, dyes having sublimation properties are more likely to appear on the surface of the resin composition. For this reason, the inhibitory effect of powder aggregation is exhibited very well in the powder of the resin composition containing these dyes.

There is no restriction | limiting in particular as resin which the powder of the said resin composition contains, 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, polyester, 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, etc. .
Any of the above-described resins may be used alone or in combination of two or more.

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. Polymer (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 copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester A copolymer etc. are mentioned.

  As an example of a commercial product of the above resin, Diacron FC-684, Diacron FC-1224, Diacron FC-316, etc. manufactured by Mitsubishi Rayon Co., Ltd., known as polyester, etc .; known as styrene-acrylate copolymer CPR-100, CPR-250, CPR-390, etc. manufactured by Mitsui Chemicals, Inc.

  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.

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. As a guide, it is usually 1 to 40%, preferably 2 to 35% 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.

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.

  The method for suppressing powder agglomeration of the present invention can suppress a phenomenon in which a dye appears on the surface of a powder of a resin composition, particularly during transportation, use or storage at a high temperature. . 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.
In the examples, the average particle size was measured using a precision particle size distribution measuring device “Multisizer 3 (manufactured by Beckman Coulter, Inc.)”.

  As an example of the powder of the resin composition, a powder toner was prepared, and the effect of suppressing the aggregation was tested.

[Preparation Example 1]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (105 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5 parts), represented by the following formula (1) Dye (5 parts), Bontron E-84 (1 part), 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 melted by a twin screw extruder. Kneaded. 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.
In addition, the dye represented by the following formula (1) was synthesized by the method described in JP-A No. 6-184481.

(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, and Titanium Industry Co., Ltd. Of SW-100 (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 yellow toner.

[Preparation Example 2]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (96 parts), C.I. I. Disperse Blue 359 (11.5 parts), a dye represented by the following formula (2) (3 parts), Bontron E-84 (1 part), and Carnauba wax C1 (4 parts) were placed in a Henschel mixer, 30 m / After premixing for 10 minutes at a rotational speed of seconds, 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 7.5 μm.
The dye represented by the following formula (2) was synthesized by the method described in JP-A-6-228444.

(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-100 (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.

[Preparation Example 3]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (105 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5 parts), Bontron E-84 (1 part) ), Carnauba wax C1 (4 parts) was 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. 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, and Titanium Industry Co., Ltd. Of SW-100 (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.

[Preparation Example 4]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (96 parts), Nippon Kayaku Co., Ltd. C.I. I. Disperse Blue 359 (11.5 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 twin screw extrusion The mixture was melt kneaded with a machine. 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 4 (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-100 (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 cyan toner containing only one type of dye.

The solubility of each dye contained in the powder of each dendritic composition prepared as described above in acetone is shown in Table 1 below.
Abbreviations in Table 1 below have the following meanings.
DsY 54: C.I. I. Disperse Yellow 54.
DsB 359: C.I. I. Disperse Blue 359.

  The aggregation property of each powder toner prepared as described above was evaluated based on the following method. The results are shown in Table 2.

[Cohesiveness evaluation test]
Weigh 5.0 g of toner in a 50 ml glass tube bottle (manufactured by Nidec Rika Glass Co., Ltd., SV-50A), seal with a cap lid, store for 24 hours under the following four conditions, and then leave it to return to room temperature. did. 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.

[Aggregation evaluation criteria]
A: Immediately after turning upside down, the toner inside is discharged by natural fall.
B: Even if it is turned upside down, it will not be discharged immediately, but it will naturally fall within 30 seconds to 1 minute.
C: Even if it passes upside down for more than 1 minute, it does not fall naturally.
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.

[Presence of agglomerates]
A: Agglomerates are not found in the powder that spontaneously falls.
B: Although the powder that has fallen naturally is slightly agglomerated, it immediately returns to powder when pressed with a finger.
C: The fallen powder 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.

  As apparent from Table 2, the powder toner of the present invention has reduced powder agglomeration from both aspects of agglomeration and agglomerate formation, and it is clear that the powder toner has an effect of suppressing powder agglomeration. became.

  Below, the preparation examples of the powder of a resin composition are described as preparation examples 5-15. The mixer used in each preparation example is BM-RS08 manufactured by ZOJIRUSHI CORP.

[Preparation Example 5]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (50.0 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 2.4 parts), the above formula ( The dye represented by 1) (2.4 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.

[Preparation Example 6]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (36.0 parts), Nippon Kayaku Co., Ltd. C.I. I. Disperse Blue 359 (2.5 parts) and the dye represented by the above formula (2) (1.5 parts) were melt-blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.
[Preparation Example 7]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts), C.I. I. Disper Thread 60 (Nippon Kayaku Co., Ltd .: 3.0 parts), C.I. I. Disperse thread 92 (manufactured by Nippon Kayaku Co., Ltd .: 2.0 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.

[Preparation Example 8]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts), C.I. I. Disper Thread 60 (Nippon Kayaku Co., Ltd .: 3.0 parts), C.I. I. Disperse thread 74 (Nippon Kayaku Co., Ltd .: 2.0 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.

[Preparation Example 9]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts), C.I. I. Disperse Blue 359 (manufactured by Nippon Kayaku Co., Ltd .: 2.5 parts) and the dye represented by formula (1) (2.5 parts) were melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.
[Preparation Example 10]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.0 parts), C.I. I. Disperse Blue 359 (Nippon Kayaku Co., Ltd .: 1.5 parts), Kaya Set Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 2.0 parts), Formula (1 ) (4.0 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.
[Preparation Example 11]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.0 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 2.0 parts), Formula (1 ) And a dye represented by the formula (2) (1.5 parts) were melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.
[Preparation Example 12]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (45.8 parts), C.I. I. Disperse Blue 359 (Nippon Kayaku Co., Ltd .: 2.1 parts), dye represented by formula (2) (1.3 parts), C.I. I. A dye (1.5 parts) represented by Solvent Blue 63 (Nippon Kayaku Co., Ltd .: 0.9 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a resin composition powder.
[Preparation Example 13]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts), Kayaset Yellow AG (Nippon Kayaku Co., Ltd., CI Disperse Yellow 54: 5.0 parts) at 220 ° C Melt blended on a heated hot plate. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a powder of a comparative resin composition.

[Preparation Example 14]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts), Nippon Kayaku Co., Ltd. C.I. I. Disperse Blue 359 (6.5 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a powder of a comparative resin composition.

[Preparation Example 15]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts), Kayaset Yellow AH (Nippon Kayaku Co., Ltd., CI Disperse Yellow 160: 2.5 parts), formula (2 ) (2.5 parts) was melt blended on a hot plate heated to 220 ° C. After cooling, the obtained kneaded product was pulverized with a mixer to obtain a powder of a comparative resin composition.

The solubility of each dye contained in the powder of each dendritic composition prepared as described above in acetone is shown in Table 3 below. In Table 1 below, “<0.01” means that the solubility in acetone is less than 0.01 g / 100 ml.
Abbreviations in Table 1 below have the following meanings.
DsY54: C.I. I. Disperse Yellow 54.
DsR60: C.I. I. Disperse thread 60.
DsR74: C.I. I. Disperse thread 74.
DsR90: C.I. I. Disperse thread 90.
DsB359: C.I. I. Disperse Blue 359.
SvB63: C.I. I. Solvent Blue 63.

  The bleeding property of the powder of each resin composition prepared as described above was evaluated based on the following method. The results are shown in Table 4.

[Bleedability test]
Each 50 g of resin composition powder is weighed into a 50 ml glass tube bottle (manufactured by Nidec Rika Glass Co., Ltd., SV-50A), sealed with a cap lid, stored under the following two conditions, and then stored at room temperature. It was allowed to stand until it returned. Thereafter, the presence or absence of bleed-out was evaluated from the electron microscope (S-4800 type field emission scanning electron microscope manufactured by Hitachi High-Technologies Corporation) photographs of the powders of the respective resin compositions 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.

[Evaluation criteria]
A: The bleed-out solid is hardly observed.
B: A bleed-out solid is observed, but most of the solids are less than 1 μm.
C: A bleed-out solid is observed, but many medium-sized solids of 1 μm or more and less than 3 μm are observed.
D: There are many solids that bleed out, and many large solids of 3 μm or more are observed.

  As is apparent from Table 4, the powder of the present invention was found to have an effect of suppressing bleed-out at high temperatures. Further, as the evaluation result of bleed-out deteriorated from A to D, the cohesiveness and the state of the coagulated mass also deteriorated, and it was confirmed that there is a correlation between the bleed-out and the cohesiveness.

  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 (1)

A method for suppressing powder aggregation in a powder of a resin composition containing at least a polyester resin and two types of dyes , wherein DsY54 is combined with Formula (1) and / or Formula (2) as a combination of the two types of dyes. ), A combination of DsB359 and Formula (1) or Formula (2), a combination of DsB359 and DsY54 and Formula (1), a combination of DsB359 and SvB63 and Formula (2), or a combination of DsR60 and DsR74 or DsR92 A method for suppressing powder aggregation , including any of the above .