JP2015131934A - Bleed-out suppression method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleed-out suppression method in powder of a resin composition that contains at least resin and dye.SOLUTION: There is provided a bleed-out suppression method in powder of a resin composition containing at least resin as well as at least two kinds of dyes having a sublimation property, in which, among the at least two kinds of dyes, at least one kind of dye is a dye having a total Hansen solubility parameter of 25.0 to 40.0 MPa1/2; thereby a powder agglomeration could be suppressed even for the case of heating under high temperatures.

Description

  The present invention relates to a method for suppressing bleeding out in a powder of a resin composition containing at least a resin and a dye having sublimation properties.

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 dye having a sublimation property as a colorant is different from other colorants, for example, during transportation, when used as a coloring material, due to long-term storage or aging, etc. Since it has been known that powder agglomeration at high temperatures is characteristic, its suppression has become an extremely important issue.
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.
Such a phenomenon is remarkably observed in a powder containing a dye having a sublimation property, and there is a strong demand for improvement in such a powder.

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 bleed-out in a powder of a resin composition containing at least a resin and a dye having sublimation properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that at least the resin and the powder of the resin composition containing at least two kinds of dyes having sublimation properties, Of these, the present invention was completed by finding that the above-mentioned problems could be solved by using at least one dye as a dye having a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2. That is, the present invention relates to the following 1).

1)
A method of suppressing bleed out in a powder of a resin composition containing at least a resin and at least two types of dyes having sublimation properties, wherein at least one type of the at least two types of dyes is A method for suppressing bleedout, wherein the dye has a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2.
2)
The method for suppressing bleeding out according to 1) above, wherein the powder of the resin composition is a toner.
3)
The bleed-out suppression method according to any one of 1) or 2) above, wherein the powder of the resin composition is a toner further containing a charge control agent and a wax.

  According to the present invention, it was possible to provide 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 having sublimation properties.

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 solves the above-mentioned problem in the powder of a resin composition containing at least a resin and one kind of dye having a sublimation property, and adds at least one kind of dye having a sublimation property to at least two kinds of dyes. And at least one of the at least two dyes is a dye having a sublimation property in which the total Hansen solubility parameter of the dye is 25.0 to 40.0 MPa1 / 2. The above-mentioned problems are solved.
The total Hansen solubility parameter is preferably 26.0-37.0 MPa1 / 2, more preferably 26.0-34.0 MPa1 / 2.
When the powder of the resin composition contains two kinds of dyes, one of the dyes is a disperse beverage or an oil-soluble dye having a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2. The remaining one kind of dye is not particularly limited. The remaining one type of dye may be various dyes described below, or a sublimable dye having a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2.
Further, the “powder” of the resin composition is used in the meaning including all powders having various shapes such as particles.

  The cause of the above-mentioned powder aggregation is due to a phenomenon in which the dye that has been uniformly melted or dispersed in the resin composition becomes non-uniform due to heat and precipitates as a solid on the surface of the resin composition, that is, bleed out. It seemed to do. The bleed-out state can be confirmed by observing the powder with, for example, an electron microscope. It was found that there was a correlation between the bleed-out state and the powder aggregation, and it was suggested that the better the bleed-out state, the less or less likely the powder aggregation. This was confirmed by an evaluation test, and it was found that powder aggregation can be suppressed by suppressing bleeding out.

The Hansen solubility parameter is known as a solubility index indicating “how much a certain substance is dissolved in a certain substance”. In the calculation, parameters relating to three kinds of interactions, van der Waals interaction (δD), electrostatic interaction (δP), and hydrogen bonding interaction (δH) are proposed. The total Hansen solubility parameter (δTot) is a value calculated in consideration of all these three types of parameters.
In this specification, the total Hansen solubility parameter means a value calculated by the Hansen solubility parameter software (HSPiP 3rd Edition 3.1.16).
The above Hansen solubility parameters can be easily calculated by those skilled in the art. As an example of a dye, the three primary colors of yellow, magenta, and cyan are listed as 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 satisfying a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2.

As the dye having the sublimation property, for example, in “Dye 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)” Examples include dyes having a heat-sensitive test (Method C) contamination (polyester) test result of preferably grade 3-4 or less; more preferably grade 3 or less. Among such known dyes, C.I. I. Examples of the dye having a number include the following dyes.
Examples of yellow dyes include C.I. I. Disperse yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; C.I. I. Solvent yellow 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; and the like.
Examples of red dyes include C.I. I. Disperse thread 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240; I. Butt 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; C.I. I. Solvent Blue 3, 63, 83, 105, 111;

At least two types of the above dyes are used in combination, but two or more types may be used (mixed) depending on 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.

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.
If the total content of the dye is less than 1%, sufficient performance as a coloring material cannot be exhibited, and if it exceeds 40%, the dye may be melted or poorly dispersed in the powder, making it difficult to suppress bleed out. 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.

There is no restriction | limiting in particular as wax, It can select suitably from well-known waxes. Among them, a wax having a melting point of usually 50 ° C. to 160 ° C., preferably 50 ° C. to 150 ° C., more preferably 50 to 120 ° C. is preferable. By containing such a wax, the resin composition powder effectively works as a release agent between the fixing roller and the toner interface, and thus oilless (for example, a release agent such as oil). Even when the agent is used in a method in which the agent is not applied to the fixing roller, the hot offset property is improved.
Examples of the wax include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as montan wax, ozokerite, and cercin; paraffin, microcrystalline, And natural waxes such as petroleum waxes such as petrolatum;
Further, for example, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers;
Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-
Homopolymer or copolymer of polyacrylate such as n-lauryl methacrylate (for example, copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); crystalline polymer having a long alkyl group in the side chain, etc. as wax It can also be used.
Any of these waxes can be used alone or in combination of two or more.
The wax content is usually 0.1 to 20%, preferably 0.5 to 10%.
When the wax content is less than 0.1%, offset to the fixing roller is likely to occur, and when it exceeds 20%, poor fixing of the powder of the resin composition to the intermediate recording medium occurs. The method for obtaining the wax is not particularly limited, and the wax can be synthesized by a known method or can be obtained as a commercial product. As an example of a commercially available product, for example, carnauba wax may be Carnauba wax C1 manufactured by Kato Yoko Co., Ltd., and montan wax may be Licowax KP manufactured by Clariant.

There is no restriction | limiting in particular as a charge control agent, It can select suitably from well-known charge control agents.
For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Or a compound thereof, tungsten simple substance or a compound thereof, fluorine-based activator, salicylic acid metal salt, salicylic acid derivative metal salt, and the like.
Any of the charge control agents can be used alone or in combination of two or more.
The content of the charge control agent varies depending on the type of the above-described resin, the presence or absence of other additives, and the like, and it is difficult to define it generally. As a standard of the content of the charge control agent, it is usually 0.1 to 10%, preferably 0.2 to the total mass of the resin containing at least the polyester resin that constitutes the powder of the resin composition. It is about 5%.
When the content of the charge control agent is less than 0.1%, the charge control performance may not be obtained. When the content exceeds 10%, the chargeability of the powder of the resin composition becomes too large. By reducing the effect, the electrostatic attractive force between the powder of the resin composition and the developing roller may increase, resulting in a decrease in fluidity of the powder and a decrease in image density.
Examples of commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, and oxynaphthoic acid metal complex Bontron E-82. Bontron E-84 of salicylic acid metal complex, Bontron E-89 of phenol condensate (above, manufactured by Orient Chemical Industries); TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, Hodogaya) Chemical Industry Co., Ltd.); quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst); LRA -901, Boron complex LR-147 (Nippon Car Tsu DOO Ltd.); copper phthalocyanine; perylene; quinacridone; azo pigments; or a sulfonic acid group, a carboxyl group, having a functional group such as quaternary ammonium salts, polymer compounds; and the like are.

Examples of external additives include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
These external additives can be hydrophobized with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Moreover, it can also process with a silicone oil as needed, and can also process under a heating. Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and epoxy / polyester. Examples thereof include ether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic-modified silicone oil, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.
The addition amount of the external additive is usually about 0.1 to 5% with respect to the total mass of the toner processed with the external additive.
The primary particle diameter of the external additive is preferably 5 nm to 2 μm, preferably 5 nm to 500 nm.
Is more preferable. The specific surface area of the external additive by BET method is preferably 20 to 500 m <2> / g.
Examples of commercially available external additives include, for example, AEROSIL R812, AEROSIL RX50, AEROSIL RX200, AEROSIL RX300, AEOSIL RX300 manufactured by Nippon Aerosil Co., Ltd., TG-6110G, TG-810G, TG-811F manufactured by Cabot Japan Co., Ltd. H2000 / 4, H2000T, H05TM, H13TM, H20TM, H30TM, etc. manufactured by Clariant Japan Co., Ltd .; AEROXIDE Alu C 805, etc. manufactured by Nippon Aerosil Co., Ltd. as alumina; STT-30A manufactured by Titanium Industry Co., Ltd. as titanium oxide EC-300, Nippon Aerosil Co., Ltd. AEROXIDE TiO2 T805, AEROXIDE TiO2 NKT90, etc .; Strontium titanate made by Titanium Industry Co., Ltd. SW-100, SW-350 and the like; and the like can be mentioned. In these, AEROSIL RX300, H05TM, TG-811F, SW-100, SW-350 etc. are preferable.
The amount of the external additive used is usually 0.01 to 5%, preferably 0.01 to 4% with respect to the total mass of the powder of the resin composition treated with the external additive.

  A powder toner can be obtained by heating or melt-kneading the above components and the like as necessary, followed by pulverization and classification. During this pulverization / classification, for example, particles of the resin composition produced by pulverization are heat-treated in a flowing state in an air flow, so that the particles with sharp corners or distorted shapes become more spherical. In other words, the so-called “spheroidizing” process can be performed.

  The bleed-out suppression method 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 at high temperature, use, or storage. For this reason, it becomes possible to suppress bleed-out 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.

[Example 1]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (43.8 parts: polyester resin), C.I. I. Disperse Yellow 54 (1.8 parts: Nippon Kayaku Co., Ltd.), C.I. I. Disperse thread 60 (1.4 parts: manufactured by Nippon Kayaku Co., Ltd.), C.I. I. Disperse Blue 72 (5.8 parts: manufactured by Nippon Kayaku Co., Ltd.) was dissolved on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Example 2]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Blue 359 (3.5 parts: Nippon Kayaku Co., Ltd.), C.I. I. Solvent Blue 63 (3.5 parts: manufactured by Nippon Kayaku Co., Ltd.) was kneaded for 1 minute by dissolving the resin and the dye on a hot plate at 220 ° C. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Comparative Example 1]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts: polyester resin), C.I. I. Disperse Yellow 54 (2.4 parts: manufactured by Nippon Kayaku Co., Ltd.) was dissolved on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Comparative Example 2]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Blue 359 (7.0 parts: Nippon Kayaku Co., Ltd.) was dissolved on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

The total Hansen solubility parameter (δTot) of each dye contained in the powder of each dendritic composition prepared as described above is shown in Table 1 below.
Abbreviations in Table 1 below have the following meanings.
DsY 54: C.I. I. Disperse Yellow 54.
DsR 60: C.I. I. Disperse thread 60.
DsB 72: C.I. I. Disperse Blue 72.
DsB 359: C.I. I. Disperse Blue 359.
SvB 63: C.I. I. Solvent Blue 63.

  The cohesiveness of the powder of each resin composition prepared as described above was evaluated based on the following method. The results are shown in Table 2.

[Bleedability test]
5.0 g of the dye resin composition is weighed into a 50 ml glass tube (manufactured by Nippon Denka Glass Co., Ltd., SV-50A), sealed with a cap lid, stored under the following two conditions, and then statically cooled to room temperature. I put it. Then, the presence or absence of bleed-out was evaluated according to the evaluation criteria of the following AD from the electron microscope (Hitachi High-Technologies Corporation make, S-4800 type field emission scanning electron microscope) photograph of the powder of each resin composition, respectively. .
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 2, the powder toner of the present invention has reduced bleeding out from both the agglomeration and the formation of aggregates, and has an effect of suppressing powder aggregation. It was.

[Example 3]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (95 parts), C.I. I. Disperse Yellow 54 (Nippon Kayaku Co., Ltd .: 1.5 parts), C.I. I. Disper Thread 60 (Nippon Kayaku Co., Ltd .: 2.0 parts), C.I. I. Disperse Blue 72 (Nippon Kayaku Co., Ltd .: 6.5 parts), Bontron E-84 (1 part), and Carnauba wax C1 (4 parts) are placed in a Henschel mixer and reserved for 10 minutes at a rotation speed of 30 m / sec. After mixing, the mixture was melt kneaded with 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 8.0 μm.

(Process 2)
Toner base particles (100 parts) obtained in 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 prepare a black toner of Example 4.

[Example 4]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (95 parts), C.I. I. Disperse Blue 359 (Nippon Kayaku Co., Ltd .: 5.0 parts), C.I. I. Solvent Blue 63 (Nippon Kayaku Co., Ltd .: 5.0 parts), Bontron E-84 (1 part) and Carnauba wax C1 (4 parts) are placed in a Henschel mixer and premixed for 10 minutes at a rotation speed of 30 m / sec. Then, the mixture was melt kneaded with 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.

(Process 2)
Toner base particles (100 parts) obtained in 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 prepare a cyan toner of Example 5.

[Comparative Example 3]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (105 parts), C.I. I. Disperse Yellow 54 (Nippon Kayaku Co., Ltd .: 5.0 parts), Bontron E-84 (1 part), and Carnauba wax C1 (4 parts) are placed in a Henschel mixer and reserved for 10 minutes at a rotation speed of 30 m / second. After mixing, the mixture was melt kneaded with 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 Comparative Example 3 (Step 1), H05TM (1.5 parts) manufactured by Clariant Japan, TG-811F (1.5 parts) manufactured by Cabot, and manufactured by 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.

[Comparative Example 4]
(Process 1)
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (96 parts), C.I. I. Disperse Blue 359 (Nippon Kayaku Co., Ltd .: 11.5 parts), Bontron E-84 (1 part) and Carnauba wax C1 (4 parts) are placed in a Henschel mixer and reserved for 10 minutes at a rotation speed of 30 m / sec. After mixing, the mixture was melt kneaded with 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 Comparative 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 toners of Examples 3 to 4 and Comparative Examples 3 to 4 obtained as described above were tested in the same manner as the “[Bleed property test]” and evaluated according to the above “[Evaluation criteria]”. did. The results are shown in Table 3 below.

  As is apparent from Table 3, the powder of the present invention has an effect of suppressing bleed out even in the state of a powder toner containing a charge control agent, wax and the like in addition to the resin and the dye. It became.

  Below, preparation of the powder of a resin composition is described as Examples 5-9 and the comparative examples 5 and 6 for a comparison. The mixer used in each preparation is BM-RS08 by Elephant Mahobin Co., Ltd.

[Example 5]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Yellow 54 (2.0 parts: Nippon Kayaku Co., Ltd.), C.I. I. Disperse thread 60 (2.0 parts: manufactured by Nippon Kayaku Co., Ltd.) was melted on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Example 6]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Blue 359 (3.0 parts: manufactured by Nippon Kayaku Co., Ltd.), C.I. I. Disperse Blue 72 (3.0 parts: manufactured by Nippon Kayaku Co., Ltd.) was kneaded for 1 minute by dissolving the resin and the dye on a hot plate at 220 ° C. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Example 7]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Yellow 54 (2.0 parts: Nippon Kayaku Co., Ltd.), C.I. I. Solvent Blue 63 (2.0 parts: manufactured by Nippon Kayaku Co., Ltd.) was kneaded for 1 minute by dissolving the resin and the dye on a hot plate at 220 ° C. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Example 8]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (44.0 parts: polyester resin), C.I. I. Disperse Blue 359 (1.0 part: Nippon Kayaku Co., Ltd.), C.I. I. Solvent Blue 63 (3.0 parts: manufactured by Nippon Kayaku Co., Ltd.), C.I. I. Disperse thread 60 (3.0 parts: manufactured by Nippon Kayaku Co., Ltd.) was melted on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Example 9]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Blue 360 (2.0 parts: manufactured by Shenzhen Technologies), C.I. I. Disperse Yellow 54 (1.0 part: Nippon Kayaku Co., Ltd.), C.I. I. Disperse thread 60 (2.0 parts: manufactured by Nippon Kayaku Co., Ltd.) was melted on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Comparative Example 5]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (52.5 parts: polyester resin), C.I. I. Disperse Yellow 54 (2.4 parts: manufactured by Nippon Kayaku Co., Ltd.) was dissolved on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

[Comparative Example 6]
Mitsubishi Rayon Co., Ltd. Diacron FC-316 (48.0 parts: polyester resin), C.I. I. Disperse Blue 359 (7.0 parts: Nippon Kayaku Co., Ltd.) was dissolved on a 220 ° C. hot plate and kneaded for 1 minute. The obtained kneaded product was pulverized with a mixer to obtain a resin composition powder containing a dye.

The total Hansen solubility parameter (δTot) of each dye contained in the powder of each dendritic composition prepared as described above is shown in Table 1 below.
The abbreviations in Table 4 below have the following meanings.
DsY 54: C.I. I. Disperse Yellow 54.
DsR 60: C.I. I. Disperse thread 60.
DsB 72: C.I. I. Disperse Blue 72.
DsB 359: C.I. I. Disperse Blue 359.
DsB 360: C.I. I. Disperse Blue 360.
SvB 63: C.I. I. Solvent Blue 63.

  The cohesiveness of the powder of each resin composition prepared as described above was evaluated based on the following method. The results are shown in Table 5.

[Bleedability test]
5.0 g of the dye resin composition is weighed into a 50 ml glass tube (manufactured by Nippon Denka Glass Co., Ltd., SV-50A), sealed with a cap lid, stored under the following two conditions, and then statically cooled to room temperature. I put it. Then, the presence or absence of bleed-out was evaluated according to the evaluation criteria of the following AD from the electron microscope (Hitachi High-Technologies Corporation make, S-4800 type field emission scanning electron microscope) photograph of the powder of each resin composition, respectively. .
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 clear from Table 5, the powder toner of the present invention has reduced bleeding out from both the agglomeration and the formation of aggregates, and it is clear that the powder toner has an effect of suppressing powder aggregation. It was. 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 bleed-out suppression method 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 (3)

  A method of suppressing bleed out in a powder of a resin composition containing at least a resin and at least two types of dyes having sublimation properties, wherein at least one type of the at least two types of dyes is A method for suppressing bleedout, wherein the dye has a total Hansen solubility parameter of 25.0 to 40.0 MPa1 / 2.   The bleed-out suppression method according to claim 1, wherein the resin composition powder is toner. The bleed-out suppression method according to claim 1 or 2, wherein the powder of the resin composition is a toner further containing a charge control agent and a wax.