JP2021139053A - Manufacturing method of dyeing body - Google Patents

Abstract

To provide a manufacturing method of a dyeing body where the transparency of a dyed image is high, with high quality and an excellent hand feeling, because the dyeing density of a body to be dyed is sufficient whilst the body to be dyed and a toner layer of an intermediate recording medium are not strongly adhered to each other.SOLUTION: A dyeing body is obtained in the following manner: after an image is formed on an intermediate recording medium by using a dry toner containing a sublimable dye, by an electrophotographic system, the intermediate recording medium faces the body to be dyed without coming contact with it, a gap having 1 μm to 150 μm between the toner adhesion surface of the intermediate recording medium and the surface of the body to be dyed is heated, and the sublimable dye in the toner adhered to the intermediate recording medium is sublimated and transferred to the body to be dyed.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a dyed product, which produces a dyed product such as a cloth by sublimation transfer using an intermediate recording medium in which an image is formed with a dry toner by an electrophotographic method.

In recent years, a sublimation transfer dyeing method using an inkjet method has become widespread. A method in which an ink containing a sublimating dye is formed on an intermediate recording medium by an inkjet printer, the intermediate recording medium and an object to be dyed such as cloth are superposed and heated, and dyeing is performed by utilizing the sublimation property of the dye. Is. Since this method can omit the engraving plate making process, which is the biggest problem of the conventional printing method, it has become possible to realize a short delivery time in addition to a high-mix low-volume production. Furthermore, since the electronic file data created on the personal computer can be used, the design can be easily created or changed. However, problems with the inkjet printer include that it takes time to print on the intermediate recording medium and that the printed intermediate recording medium contains water and therefore requires a drying step. Therefore, although the production efficiency is significantly improved as compared with the conventional printing method, further simplification of the process and improvement of production efficiency are issues.

The sublimation transfer dyeing method using the electrophotographic method is attracting attention because the image formation on the intermediate recording medium can be performed quickly, the intermediate recording medium does not need to be dried, and the process can be simplified (patented). References 1 and 2).

However, when an image is formed on an intermediate recording medium with a dry toner containing a sublimation dye and the sublimation transfer is performed by superimposing the image on an object to be dyed such as a resin plate or a cloth, the temperature rises to a high temperature of about 200 ° C. in the sublimation transfer process. Since it is heated, the toner melts and sticks to the object to be dyed, and a part of the melted toner remains on the surface of the object to be dyed. Further, when the intermediate recording medium is peeled off from the object to be dyed after sublimation transfer, minute fragments of toner are generated and adhere to the fibers due to electrostatic force or the like. As a result, there is a problem that quality such as transparency of the dyed image deteriorates. In severe cases, the feel (texture) of the object to be dyed may be deteriorated.

Regarding this problem, in Patent Document 1, a polyester resin is used as a first component as a binder resin for a toner containing a sublimating dye, and a crosslinked structure is formed by reacting with a carboxyl group or the like of the polyester resin as a second component. The polymer that forms the above is used. By making the toner a high-density crosslinked structure, the decrease in melt viscosity of the toner during sublimation transfer is suppressed, and the generation of toner debris during peeling after sublimation transfer is also prevented, so that the quality of friction fastness is improved. The content of improvement is disclosed. However, in this method, the fixability of the toner to the intermediate recording medium becomes a problem. Otherwise, the fuser temperature needs to be fairly high, which puts a load on the electrophotographic apparatus itself and may contaminate the area around the fuser with the sublimated dye.

Further, when the intermediate recording medium is peeled from the cloth after the sublimation transfer, the intermediate recording medium and the cloth may be firmly adhered to each other depending on the type of the cloth, which may make the peeling difficult.

Regarding this problem, in Patent Document 2, when sublimation transfer is performed using a dry toner containing a sublimation dye, a polyester resin exhibiting a specific dynamic viscoelastic behavior is used as the binder resin used for the toner. Therefore, it is disclosed that the sticking strength between the fabric and the intermediate recording medium at the time of sublimation transfer can be relaxed, the peeling can be easily performed, and uneven dyeing can be prevented. However, the document does not describe measures for friction fastness, and it remains an issue.

Further, when the object to be dyed is not a cloth, for example, in tableware such as a mug coated with polyester resin, the toner component melted at the time of sublimation transfer adheres to the surface of the mug and remains, and the surface of the mug becomes glossy. It may disappear and give a rough feeling, which is not preferable, and there is a concern about safety due to the remaining toner component coming into contact with food.

As an example of sublimation transfer without superimposing the intermediate recording medium and the object to be dyed, in Patent Document 3, the image formed on plain paper with colorless toner is transferred by facing the image formed with sublimation dye toner in a non-contact manner. It has been shown that the color development of the dye can be achieved on plain paper. However, since this method dyes a colorless toner resin, it cannot be applied to a resin plate, a cloth, or the like.

As an example of performing sublimation transfer on a non-dyed material containing a resin plate in a non-contact manner, in Patent Document 4, a state in which the dye-adhered surface is non-contacted and separated from the resin plate or the like by 0.1 mm to 15 mm by a special transfer device. It is disclosed that a high-concentration and uniform dyeing can be achieved by facing each other and dyeing while sweeping. However, this method requires the preparation of a special transfer device. Further, although a uniform high density can be obtained by this method, it is not possible to reproduce an image with fine details such as fine lines.

Japanese Patent No. 6250218 Japanese Unexamined Patent Publication No. 2016-16517 Japanese Unexamined Patent Publication No. 63-63060 Japanese Patent No. 5735762

The present invention is a method for producing a dyed product, which is a method for producing a dyed product dyed on a resin plate, a cloth, or the like by sublimation transfer using an intermediate recording medium in which an image is formed with a dry toner containing a sublimating dye. The dyeing concentration of the object is sufficient, the object to be dyed and the toner layer of the intermediate recording medium do not adhere firmly during the sublimation transfer process, and the dyed image has high transparency and good quality, giving a feeling of touch. It is also an object of the present invention to provide an excellent method for producing a dyed product. In addition, even when the object to be dyed is tableware, etc., the toner component is prevented from adhering to the dyed object after sublimation transfer, and the gloss is not deteriorated or the feeling of roughness is not generated, and the safety of foods to be contacted is improved. It is an object of the present invention to provide a method for producing a dyed product, which can produce a dyed product without any concern.

As a result of diligent studies to solve the above problems, the present inventors formed an image on an intermediate recording medium using a dry toner containing a sublimative dye, and then applied the intermediate recording medium to an object to be dyed. The toner adhered to the intermediate recording medium by being heated in a state where the gap between the toner adhesion surface of the intermediate recording medium and the surface of the object to be dyed is 1 μm to 150 μm. By sublimating and transferring the sublimating dye inside to the object to be dyed to obtain a dyed product, the dyed product has a sufficient dyeing concentration, and the dyed image has high transparency, excellent quality, and does not impair the feel of the dyed product. Succeeded in obtaining, and completed the present invention. Also, when the dyed product is tableware, etc., it is difficult for the dyed product to come into direct contact with the intermediate recording medium image-formed with dry toner during sublimation transfer, so the safety of food products, etc. that come into contact with the dyed product during use. It turned out that the concern disappeared.

In the first aspect of the present invention to achieve the above object, an image is formed on an intermediate recording medium using a dry toner containing a sublimation dye by an electrophotographic method, and then the intermediate recording medium is applied to an object to be dyed. The toner adhered to the intermediate recording medium was heated in a state where the gap between the toner adhesion surface of the intermediate recording medium and the surface of the object to be dyed was 1 μm to 150 μm. A method for producing a dyed product, which comprises sublimating and transferring the sublimating dye in the dye to the object to be dyed to obtain a dyed product.

A second aspect of the present invention is the method for producing a dyed product according to the first aspect, wherein a spacer is sandwiched between the intermediate recording medium and the dyed product to form the gap. It is in the manufacturing method.

A third aspect of the present invention is the method for producing a dyed product according to the second aspect, wherein the spacer is made of a filter material that allows the sublimation dye to permeate.

A fourth aspect of the present invention is the area A1 of the member forming the filter medium obtained from an image of the filter medium placed on a predetermined background in the method for producing a dyed product according to the third aspect. The method for producing a dyed product is characterized in that the projected area ratio represented by the following formula (1) is 99% or less using the background area A2.
Projected area ratio (%) = A1 / (A1 + A2) Equation (1)
A1: Area of the member forming the filter medium (mm ² )
A2: Background area (mm ² )

A fifth aspect of the present invention is the method for producing a dyed product according to the third or fourth aspect, wherein the projected area ratio of the filter medium is 91% or less.

A sixth aspect of the present invention is characterized in that, in the method for producing a dyed product according to any one of the third to fifth aspects, the filter medium is selected from Japanese paper, a non-woven fabric sheet, a cloth, and a heat-resistant resin mesh sheet. It is in the manufacturing method of the dyed product.

In the method for producing a dyed product of the present invention, during sublimation transfer, the dyed product such as a resin plate or cloth is not brought into contact with the toner-adhered surface of the intermediate recording medium, and a gap having a distance of 1 μm to 150 μm between the two is not brought into contact with each other. It is characterized in that it is heat-treated in the state where the above is formed. According to this method, a dyed image having a sufficient density is formed on a dyed object such as a resin plate or a cloth, and the dyed product and the toner layer of the intermediate recording medium do not firmly adhere to each other. It has the effect of obtaining a dyed product having high transparency and good quality of the dyed image, excellent touch feeling, and no concern about the safety of foods and the like that come into contact with it.

It is a micrograph of the filter material of Example 5. It is a micrograph of the filter material of Example 6. It is a micrograph of the filter material of Example 7. It is a micrograph of the filter material of Example 8. It is a micrograph of the filter material of Example 9. It is a micrograph of the filter material of Example 10. It is a micrograph of the filter material of Example 11. It is a micrograph of the filter material of Example 12. It is a micrograph of the filter material of Comparative Example 4.

Hereinafter, the present invention will be described in detail.
In the present invention, there are a plurality of methods for heating in a state where the gap between the toner adhesion surface of the intermediate recording medium and the surface of the object to be dyed is 1 μm to 150 μm, and any of them may be used. That is, nothing may be arranged in the gap, or a spacer through which the sublimation dye can pass may be arranged in the gap.

As a specific example in which nothing is arranged in the gap, for example, a device is used in which an intermediate recording medium is attached and held on a flat plate heater that can be heated, and the object to be dyed is held facing a stage whose position can be adjusted at a minute distance. , It can be carried out by heating the flat plate heater in a state where a gap having a predetermined size is provided and held.

On the other hand, when heating with a spacer sandwiched between the toner adhesion surface of the intermediate recording medium and the object to be dyed, the existing pressure-heating sublimation transfer press can be used, which is particularly practical. be. The gap in this case is formed corresponding to the thickness of the spacer sandwiched between the toner adhesion surface of the intermediate recording medium and the object to be dyed.

Such a spacer is not particularly limited as long as it is sandwiched between the toner adhesion surface of the intermediate recording medium and the object to be dyed and can form a gap of 1 μm to 150 μm.

As the spacer, for example, a filter material in which fine fibers are formed into a lattice shape or a net shape can be used. Since such a filter material requires a path through which the sublimation dye is transmitted and sublimation transfer is required, the projected area ratio of the sandwiched surface needs to be 99% or less. The projected area ratio will be described later.

Even when a filter material with a projected area ratio of 99% or less is sandwiched, fibers are caught in the path of sublimation transfer of the dye and the transfer efficiency drops, but there is no problem in practical use by optimizing the conditions such as heating time. Can be obtained.

The projected area ratio of the filter medium used in the present invention can be used as long as it is 99% or less, preferably 91% or less, and more preferably 90% or less.

In the present invention, the projected area ratio of the filter material is such that the filter material is placed against the background of a color that can be easily distinguished from the color of a member such as a fiber constituting the filter material, a 200-fold optical microscope photograph is taken, and the photograph is taken as an image. It was calculated by the following formula (1) during the analysis.
Projected area ratio (%) = A1 / (A1 + A2) Equation (1)
A1: Area of filter media fiber (mm ² )
A2: Background area (mm ² )

Typical examples of the filter medium used in the present invention are thin paper, non-woven fabric, and net having a thickness of 1 μm to 150 μm and a projected area ratio of 99% or less. Since such a filter medium receives heat of 180 ° C. to 220 ° C. during sublimation transfer, it is necessary to use a filter medium made of a material that does not deform, deteriorate, or break at such a high temperature.

Specifically, Japanese paper, non-woven fabric sheets such as tissues and wipers, cloths such as gauze, and meshes made of heat-resistant resin such as PFA (perfluoroalkoxyalkane) can be used.

Further, when the filter material contains a material that is easily dyed with a sublimation dye such as a polyester material, the sublimation dye may be dyed on the filter material and the concentration of the dyed product may be reduced, which is not preferable. From this point of view, the non-woven fabric containing polyester is particularly easy to be dyed, and should be avoided if possible. As an index of such ease of dyeing, the dyeing concentration at close contact can be mentioned, and it is preferable to use a material having a dyeing concentration of 0.5 or less, preferably 0.4 or less. Therefore, PFA and cellulose are preferable as materials, but cellulose is preferable from the viewpoint of cost. Further, as the filter material of the cellulose material, paper such as Japanese paper, particularly Japanese paper is preferable.

When the filter medium fiber is thick, even if the projected area ratio is 99% or less, the dye is difficult to diffuse to the concealed portion by the fiber, and the dyed image may be whitened, which is not preferable. In order to obtain a stained image with few defects, the thicker the fiber, the longer it takes to obtain a predetermined concentration, which is not preferable. Therefore, in the case of a filter agent composed of fibers, the thickness of the fibers is 100 μm or less. Is preferable. In the case of paper or the like, the weight per unit area is used as an index of thickness, and paper of 10 g / m ² or less, particularly Japanese paper, is preferable.

The method for producing a dyed product of the present invention is to obtain a dyed product by dyeing the dyed product by a sublimation transfer dyeing method. Hereinafter, the sublimation transfer dyeing method will be described.

[Sublimation transfer dyeing method]
In the sublimation transfer dyeing method, first, an image is formed on an intermediate recording medium with a sublimation transfer toner using a printer or a multifunction device having an electrophotographic method. Next, the heat treatment is performed over a predetermined temperature and time with a gap of 1 μm to 150 μm formed without contacting the image forming surface of the intermediate recording medium with the object to be dyed such as a resin plate or cloth. This will be described in detail below.

The electrophotographic color printer or color multifunction device used in the sublimation transfer dyeing method is not particularly limited, and a printer / multifunction device on the market can be used. The development method is not limited, and either the non-magnetic one-component development method or the two-component development method can be used. Further, a printer or the like corresponding to A0 size to A4 size can be selected according to the area of dyeing.

The intermediate recording medium (transfer paper) for fixing the toner image in the present invention is not particularly limited as long as the toner can be fixed by an electrophotographic printer or the like and is stable when heat-treated in the sublimation transfer step described later. For example, in "Paper / Paperboard and Pulp Terms" JISP 0001: 1998 (confirmed in 2008, revised on March 20, 1998, published by the Japanese Standards Association) ", pages 28-47," 3. Classification f) Paper / paperboard varieties and processed products described in "Paper / paperboard varieties and processed products" (No. 6001-6284. However, No. 6235 "Oil resistance", 6263 "Flute, step", 6273 "Pulp molding""Products", 6276 "Carbon Paper", 6277 "Multicoview Foam Paper", 6278 "Back Carbon Foam Paper"); and Cellophane (hereinafter, "Paper / Paperboard Types and Processed Products; and Cellophane" It can be appropriately selected from "paper, etc."). However, commercially available copy paper (PPC paper) can be used without any problem. However, when using an intermediate recording medium that allows the sublimation dye to permeate and strike through during sublimation transfer, a sheet that can prevent the dye from permeating (for example, cooking paper or Hashima base paper) is stacked. Therefore, it is necessary to prevent dye contamination of the sublimation transfer device. In addition, from the viewpoint of preventing strike-through of sublimation dyes, the intermediate record was adjusted to a ^{density of 1 g / cm 3} or more by optimizing the pulp material, filler, surface coating agent, beating / pressing processing conditions, etc. It is preferable to use a medium.

Examples of the object to be dyed include fabrics composed of hydrophobic fibers or blended fibers containing hydrophobic fibers, films and plastic sheets containing hydrophobic resins, fabrics coated with hydrophobic resins, films, and plastic sheets. Examples include glass, metal, and ceramics. Examples of these hydrophobic fibers and hydrophobic resins include polyester fibers and polyester resins, and the content thereof is preferably 70% to 100%, more preferably 80% to 100%.

Examples of the above-mentioned fabric containing polyester fiber as a main component include satin, tropical, double picket, microfiber and the like.

As the sublimation transfer dyeing method in the present invention, a conventionally known method can be used except that a gap of 1 μm to 150 μm is provided between the toner adhesion surface of the intermediate recording medium and the object to be dyed, and a constant temperature and constant temperature can be used. It is heat treated in the heating time. When using a sublimation transfer device in which a conventionally known intermediate recording medium and an object to be dyed are superposed on each other, a spacer such as a filter medium may be sandwiched between them, and then heat treatment may be performed by applying a constant pressure.

The dedicated sublimation transfer device includes a continuous sublimation transfer device using a drum-type heater (for example, HSR-600R manufactured by Hashima Co., Ltd.), and an intermediate recording medium (transfer paper) and cloth for sublimation transfer one by one. There are flat sublimation transfer devices (for example, HSP-126FA manufactured by Hashima Co., Ltd., NAP-502 manufactured by Asahi Textile Machinery Co., Ltd., etc.) that are cut and superposed. Furthermore, there are vacuum sublimation transfer devices (for example, HSP-1513PV-AT manufactured by Hashima Co., Ltd., STP-800 manufactured by Asahi Textile Machinery Co., Ltd.) capable of promoting the sublimation of dyes under reduced pressure, which can be selected according to the application and size. can.

Examples of the sublimation transfer device for mugs include a mug press machine PT1-B for sublimation printing manufactured by Piotec.

The heating temperature at the time of sublimation transfer is generally 180 ° C. to 220 ° C., more preferably 190 ° C. to 210 ° C. from the viewpoint of the sublimation temperature of the sublimation dye and the prevention of thermal decomposition of the object to be dyed such as cloth. be. The heating time is from 30 seconds to a maximum of about 10 minutes, and can be adjusted according to the application and workmanship in consideration of the type of the object to be dyed.

By the above heat treatment, the sublimation dye molecules contained in the toner image-formed on the intermediate recording medium are vaporized, move through the gaps of 1 μm to 150 μm, and enter the gaps of the molecular chains of the object to be dyed. Is dyed. After the heating time has elapsed, the intermediate recording medium is peeled off after cooling to room temperature, sublimation transfer dyeing is completed, and a dyed product is obtained.

In the sublimation transfer dyeing method described above, the toner for sublimation transfer that forms an image on the intermediate recording medium can be a toner that is usually used, and is not particularly limited, but an example of a method for producing the toner for sublimation transfer is shown below. However, the sublimation transfer toner will be described.

[Manufacturing method of toner for sublimation transfer]
The method for producing the sublimation transfer toner used in the present invention includes at least a binder resin and a sublimation dye, and other raw materials such as a charge control agent, a wax, and an external additive are not particularly limited, and can be used as a toner raw material. A known one can be used. Further, the production method is not limited, and the toner may be produced by a kneading and pulverizing method, or may be a toner produced by a polymerization method.

The general manufacturing method of the sublimation transfer toner by the kneading and pulverizing method will be described below. The sublimation transfer toner that can be used in the present invention is not limited to the following description.

[Bundling resin]
Examples of the binder resin used in the sublimation transfer toner include polyester-based resin, polyamide-based resin, acrylic resin, styrene-acrylic copolymer, and the like, and among these, polyester-based resin is preferable.

Examples of the raw material monomer for polyester include a polyhydric alcohol having a divalent value or higher and a polyvalent carboxylic acid compound having a divalent value or higher.

Examples of the divalent alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl). Examples thereof include alkylene oxide adducts of bisphenol A such as propane, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, bisphenol A and the like.

Examples of trihydric or higher alcohols include sorbitol, pentaerythritol, glycerose, trimethylolpropane and the like.

These divalent or higher polyhydric alcohols can be used alone or in combination of two or more.

Examples of the divalent carboxylic acid compound include dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acid, n-dodecenyl succinic acid, isododecenyl succinic acid and n-dodecyl succinic acid. Acids, isooctenyl succinic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms such as isooctyl succinic acid or an alkenyl group having 2 to 20 carbon atoms, and anhydrides or lower alkyl (carbon numbers) of these acids. 1 to 3) Esters and the like can be mentioned. Preferred examples include maleic acid, fumaric acid, terephthalic acid, and succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms.

Examples of trivalent or higher valent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and their acid anhydrides, lower alkyl. Examples thereof include (1 to 3 carbon atoms) esters. Of these, trimellitic acid and its anhydride are preferably used because they are inexpensive and reaction control is easy.

These divalent or higher valent carboxylic acid compounds can be used alone or in combination of two or more.

The glass transition temperature of the polyester resin is preferably 50 ° C. to 75 ° C., more preferably 55 ° C. to 70 ° C. Within this temperature range, the heat-resistant storage stability of the toner can be maintained in a stable state without impairing the fixability of the toner to the intermediate recording medium (transfer paper).

[Sublimation dye]
The sublimation dye used for the sublimation transfer toner is not particularly limited, and a known sublimation dye can be used. For example, the following sublimable dyes can be mentioned.

As a red dye, C.I. I. Disperse threads 4, 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 73, 75, 92, 93, 146, 152, 158, 177, 190, 190: 1, 207, 239, 240, 343, C.I. I. Bat Red 41 and the like can be mentioned.

As a blue dye, C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55, 56, 58, 60, 60: 2, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131 , 141, 145, 359, 360, C.I. I. Examples thereof include Solvent Blue 3, 63, 83, 105 and 111.

As a yellow dye, C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86, C.I. I. Examples thereof include Solvent Yellow 114 and 163.

Examples of orange dyes include C.I. I. Disperse orange 1, 1: 1, 5, 20, 25, 25: 1, 33, 56, 76 and the like can be mentioned.

As a brown dye, C.I. I. Disperse brown 2 and the like can be mentioned.

Violet dyes include C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57 and the like can be mentioned.

The above dyes may be used alone or in combination of two or more.

The black dye can be obtained by appropriately blending a yellow dye and a red dye with the blue dye as the main component. Further, in order to finely adjust the color tone, an orange dye, a brown dye, a violet dye or the like may be added in addition to the above dyes.

[wax]
The sublimation transfer toner can contain wax as a release agent for the fixing portion in order to obtain a good fixing image.

As the wax used for the sublimation transfer toner, all waxes known for the toner can be used, and the wax is not particularly limited. For example, natural waxes such as carnauba wax, rice wax and candelilla wax, paraffin wax, polyolefin wax, microcrystallin wax, Fishertropch wax, polyethylene wax, polypropylene wax, hydrocarbon wax such as ethylene-propylene copolymer, etc. Examples thereof include synthetic ester waxes, amide waxes, higher fatty acids, long chain alcohols, ketones, ethers and derivatives such as graft compounds and block compounds thereof synthesized from long chain fatty acids and long chain alcohols. These waxes may be used alone or in combination of two or more. Considering the dispersibility of the wax with respect to the polyester resin, at least one kind is a wax having a polar group, for example, carnauba wax, rice wax, candelilla wax, synthetic ester wax, paraffin wax whose molecular end is acid-modified or alcohol-modified, polyethylene wax. , Polypropylene wax or the like is preferably used.

The content of wax in the toner is preferably 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the binder resin. When the wax content is in the above range, the wax dispersibility can be improved, and good fixability and offset performance can be exhibited even in printing with a copying machine or a printer.

[Charge control agent]
A charge control agent can be blended in the sublimation transfer toner. As a result, it is possible to adjust the optimum toner charging amount according to the developing system and to stabilize the toner charging characteristics at low temperature and low humidity and at high temperature and high humidity.

As the charge control agent, known ones can be used, and a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable.

Organic metal complexes and chelate compounds are effective as charge control agents for controlling the toner to be negatively charged, and are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, aromatic dicarboxylic acid metal complexes, and organic boron. Compounds, calix-alene compounds, fluorine-containing quaternary ammonium salt compounds, polycondensates obtained by polycondensation reaction of phenols and aldehydes, etc. are used. These charge control agents may be used alone or in combination of two or more.

Examples of the charge control agent for controlling the toner to be positively charged include a niglosin dye, a triphenylmethane dye, a quaternary ammonium salt, a polymerizable monomer such as styrene, an acrylic acid ester, and a methacrylic acid ester, and a quaternary ammonium salt. A copolymer (charge control resin) with a vinyl-based monomer containing the mixture is used. These charge control agents or charge control resins may be used alone or in combination of two or more.

[Kneading process]
In the sublimation transfer toner, raw materials such as binder resin, sublimation dye, wax, charge control agent, and other various dispersants may be premixed in advance with a Henschel mixer, a ball mill, or the like, and then melt-kneaded. preferable.

The melt kneading of raw materials is not particularly limited as long as it is a facility that can be used for kneading general toners. Can be done.

Regarding the conditions of melt-kneading, if the temperature of the kneaded product is too high, the volatilization of the sublimation dye may be accelerated depending on the type of sublimation dye, so the temperature of the kneaded product immediately after kneading should be 180 ° C or less. It is preferable to knead. More preferably, the conditions are 170 ° C. or lower.

Next, the obtained kneaded product is cooled by rolling, using a cooling belt or the like, and roughly pulverized to a size of about 0.05 mm to 3 mm in order to efficiently carry out the pulverization step.

[Crushing / classification process]
Next, the coarsely pulverized kneaded product is pulverized and classified to obtain a predetermined particle size distribution. As the crusher, a conventionally known device for toner can be used, and a mechanical crusher (for example, a Cryptron system manufactured by EarthTechnica Co., Ltd., a turbo mill manufactured by Turbo Industries Co., Ltd., etc.) or a jet crusher using compressed air (for example, a jet crusher) can be used. A counter jet mill manufactured by Hosokawa Micron, etc.) can be used. It is preferable to process the crushed toner with a mechanical crusher rather than a jet crusher because crushing with a mechanical crusher can make the circularity appropriately uniform.

By classifying the pulverized toner particles in the classification step, toner particles having a sharp particle size distribution can be obtained. As the classifier, a conventionally known device can be used, and an airflow type classifier using inertial force (for example, an elbow jet manufactured by Nittetsu Mining Co., Ltd.) and a classifier having a blade rotating body (for example, TSP manufactured by Hosokawa Micron Co., Ltd.) can be used. , TTSP) and the like can be used.

The volume-based median diameter D50 of the toner after classification is preferably 4 μm to 10 μm, and more preferably 5 μm to 9 μm. The medium diameter D50 based on the volume of the toner is measured using a multisizer 3 manufactured by Beckman Coulter.

[External process]
In the sublimation transfer toner, inorganic fine particles, organic fine particles, and the like can be added as an external additive to the toner after the classification heat treatment step. As these external additives, those known for toner applications can be used without particular limitation, but the charging characteristics, fluidity, durability, developability, transferability, abrasives, lubricants, and storage stability of the toner can be used. It is preferable to select and use it as appropriate according to the purpose.

Examples of the inorganic fine particles include fine particles such as silica, titanium oxide, aluminum oxide, strontium titanate, barium titanate, zinc oxide, and cerium oxide. In addition, these inorganic fine particles can be hydrophobized according to the above purpose. As the hydrophobizing agent, known silicone oils, silane coupling agents and the like as surface treatment agents for toner external additives are used, and they may be treated alone or in combination. These silicone oils and silane coupling agents may be modified with various functional groups. Especially in the case of positively charged toner, inorganic fine particles surface-treated with an amino group-modified silicone oil or an aminosilane coupling agent or the like may be used. It is preferable to use it.

Examples of the organic fine particles include organic resin fine particles such as polymethylmethacrylate fine particles and styrene-acrylic fine particles, metallic soaps such as zinc stearate, polyvinylidene fluoride fine particles, and Teflon (registered trademark) fine particles.

In addition, as a mixer used for externally adding an additive such as inorganic fine particles or organic fine particles to the toner matrix particles, a high-speed stirrer (Henshell mixer manufactured by Nippon Coke Co., Ltd., Super mixer manufactured by Kawata Co., Ltd., etc.), a ball mill, etc. A stirring device for dry mixing such as a V-type blender is used. Further, when using the stirring device, it is preferable to increase the peripheral speed of the stirring tool or lengthen the stirring time in order to sufficiently adhere the external additive to the toner particles.

Further, the toner particles may be thermally sphericalized for the purpose of controlling the shape of the toner and modifying the surface. As a thermospherical processing apparatus for toner, Meteole Invo manufactured by Nippon Pneumatic Co., Ltd. is known.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Evaluation of resin adhesion to dyed products]
The degree of resin adhesion to the dyed object is 300% in a circle with a diameter of 1 mm using a transparent PET sheet (for OHP film color laser printer & copier manufactured by 3M Japan) as the object to be dyed. The transparency of the dyed product when the composite black toner layer (100% cyan + 100% magenta + 100% yellow) was transferred was evaluated.

The transparency was evaluated by visual judgment and by measuring the visible light absorption spectrum of the dyed transparent sheet. In the composite black dyed image, if there is no resin adhesion, the absorption at the infrared wavelength of 800 nm is almost zero. When a small amount of the resin component is attached, the incident light is scattered in the entire wavelength range, so that apparent absorption occurs even at 800 nm. At this time, it looks white and cloudy visually. When the absorbance at 800 nm was ε800, it was evaluated according to the following criteria:
ε800 <0.05 ○ No adhesion ε800 = 0.05 to 0.20 △ Although it is slightly attached, it can withstand practical use ε800> 0.20 × (Paper of the intermediate recording medium is stuck, so it is accurate Absorbance could not be measured)

[Measurement of image density of dyed fabric]
A polyester fiber cloth (tropical) was used as the object to be dyed, and a Macbeth densitometer (RD-19 manufactured by Macbeth) was used as a density measuring machine to measure the density of a 100% solid image of each color on the cloth. .. The evaluation of the image density on the fabric is as follows.
1.00 or higher Good 0.60 to 1.00 Concentration is slightly low, but can be put into practical use by adjusting transfer conditions Less than 0.60 Concentration is too low to be practical

[Evaluation of fine line reproducibility]
A cross-shaped image is formed on the intermediate recording medium with thin lines of 100% cyan and 0.2 mm in width, and a transparent PET sheet (for OHP film color laser printer & copier manufactured by 3M Japan) is used as the object to be dyed. The transfer was made so that the above-mentioned cross was included in a 1 mm circle. A 200-fold optical micrograph was taken with the dyed transparent sheet stacked on a blank sheet of paper, and the line width was measured by image analysis. The average value of each vertical and horizontal line width was recorded, and the judgment was made as follows:
0.20mm to 0.25mm Good 0.25mm to 0.40mm Somewhat blurred, but usable 0.40mm or more is too blurry and not practical

[Measurement of stained image density of filter media after use in dyeing]
Peel off the filter medium used to measure the image density of the fabric from the intermediate recording medium (using a knife if it is stuck), and stack the side facing the intermediate recording medium on a blank sheet of paper. Using a Macbeth densitometer (RD-19 manufactured by Macbeth), the density of a 100% solid image of each color on the filter medium was measured. To correct the original color of the filter media, the unused filter media was measured in the same manner and subtracted from the solid image density. The evaluation of the image density on the filtered medium after the correction is as follows.
0.20 or less Good 0.20 to 0.50 Dyeing of the filter medium is conspicuous, but practically possible 0.50 or more It is impractical because it inhibits transfer to the object to be dyed too much.

[Manufacturing of sublimation transfer toner for cyan]
Polyester resin A (Tg: 62.3 ° C., softening point: 134.0 ° C., molecular weight Mn: 4100, Mw: 142900, THF insoluble content 5%, acid value: 6.0 mgKOH / g) was 90.5% by weight, As a sublimation dye, C.I. I. Disperse Blue 359 (manufactured by Kiwa Chemical Industries, Ltd.) is 7.0% by weight, Viscol 660P (manufactured by Sanyo Chemical Industries, Ltd., melting point: 137.5 ° C.) is 2.0% by weight as wax, and TN-105 as a charge control agent. (Hodogaya Chemical Co., Ltd.) is weighed by 0.5% by weight, and these are mixed with a Henshell mixer (manufactured by Nippon Coke Industries Co., Ltd.) for 3 minutes, and then melt-kneaded by a twin-screw extruder (PCM30 manufactured by Ikekai Co., Ltd.). rice field. The temperature of the kneaded product at the outlet of the twin-screw extruder was 164 ° C. After cooling the obtained kneaded material, it is crushed and classified using a mechanical crusher (Cryptron KTM-0 manufactured by EarthTechnica Co., Ltd.) and an air flow classifier (Elbow Jet manufactured by Nittetsu Mining Co., Ltd.) to obtain a volume. A powder having an average particle size of 8.0 μm and a sharp particle size distribution was obtained.

Hydrophobized silica RX-50 (manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 40 nm, surface hydrophobization treatment: hexamethylene disilazane) was hydrophobized to 1.5 parts by weight on 100 parts by weight of the obtained powder. Silica TG-308F (manufactured by Cabot Corporation, average primary particle size: 12 nm, surface hydrophobization treatment: dimethyl silicon oil) is added in an amount of 1.0 part by weight and mixed with a Henschel mixer at a peripheral speed of 40 m / s for 3 minutes. , Manufactured sublimation transfer toner for cyanide.

[Manufacturing of sublimation transfer toner for magenta]
Same except that 6% of Dispersed Red 60 (manufactured by Kiwa Kagaku Kogyo Co., Ltd.) is used as a sublimation dye for magenta from the sublimation transfer toner for cyan, and the polyester resin A is 91.5% for blending adjustment. A sublimation transfer toner for magenta was manufactured by a manufacturing method.

[Manufacturing of sublimation transfer toner for yellow]
From the sublimation transfer toner for cyan, 3% of Disperse Yellow 54 (manufactured by Kiwa Kagaku Kogyo Co., Ltd.) is used as a sublimation dye for yellow, and polyester resin A is 94.5% for blending adjustment. A sublimation transfer toner for yellow was manufactured by the same manufacturing method.

[Manufacturing of sublimation transfer toner for black]
From the sublimation transfer toner for cyan, 10.0% of KAYADIGITAL BLACK SNC-02 (manufactured by Nippon Kayaku Co., Ltd., a mixture of multiple sublimation dyes) is used as a sublimation dye for black, and polyester is used for blending adjustment. A sublimation transfer toner for black was produced by the same production method except that the resin A was 87.5%.

[Toner image formation on an intermediate recording medium using an electrophotographic printer]
Using an electrophotographic printer equipped with a non-magnetic one-component development method, a 100% solid image of each color, a composite black image (100% cyan + 100% magenta + 100% yellow), and a line with 100% cyan are used on an intermediate recording medium. An intermediate recording medium in which a thin cross-shaped line having a width of 0.2 mm was formed and a toner layer was formed was prepared. At this time, the indoor environment was controlled to a temperature of 20 ° C. to 25 ° C. and a relative humidity of 40% to 60%.

As the intermediate recording medium, commercially available A4 copy paper (Askul Multi-Paper Super Economy +) was used.

[Sublimation transfer]
In the sublimation transfer, Examples 1 to 3, 5 to 12 and Comparative Example 1 are used with an intermediate recording medium on which a toner image is formed and an object to be dyed (transparent PET sheet and tropical) according to each evaluation content. , 2 and 4 were carried out using a flat sublimation transfer device (HSP-126FA manufactured by Hashima Co., Ltd.) under ^{the conditions of a set temperature of 205 ° C., a set pressure of 233 g / cm 2} , and a time of 60 seconds. At this time, sublimation transfer was performed by sandwiching the spacers of Examples and Comparative Examples shown below between the intermediate recording medium and the object to be stained.

In Examples 1 to 12 and Comparative Examples 1 to 4, sublimation transfer was performed using the spacers shown in Table 1. Tables 2 to 4 show the density of spacers used for sublimation transfer and the evaluation results thereof.

Further, the micrographs of the filter media used in Examples 5 to 12 and Comparative Example 4 are shown in FIGS. 1 to 9.

In Example 4 and Comparative Example 3, sublimation transfer was performed by adjusting the size of the void with a height gauge without using a spacer. In Comparative Example 1, sublimation transfer was performed using the above-mentioned flat sublimation transfer device in a state where the toner adhesion surface of the intermediate recording medium and the object to be dyed were overlapped so as to be in contact with each other without using a spacer.

Further, in Examples 1 to 3 and Comparative Example 2, the metal foils of the types shown in the table were used by making a circular hole with a diameter of 1 mm for a transparent PET sheet and a diameter of 4.5 mm for a cloth. bottom.

In Example 4 and Comparative Example 3, the intermediate recording medium was fixed to a hot plate (HP2020 type manufactured by AS ONE) so that the toner surface was vertically upward, and the object to be stained was placed on the probe of the digital force gauge (DS2-5N manufactured by Imada). After fixing, the above-mentioned force gauge is fixed to a height gauge (HDS-20C manufactured by Mitutoyo) so that the probe faces vertically downward, and the intermediate recording medium and the object to be dyed come into contact with each other and the pushing force measured by the force gauge is 10 g / The ^{height exceeding cm 2} is set to 0.00 mm, and while measuring the height with a height gauge, the hot plate is heated vertically upward with the distances shown in Tables 2 to 4 apart. Sublimation transfer was performed by holding the above-mentioned position until 60 seconds had passed after the temperature exceeded 200 ° C.

The intermediate recording medium was opposed to the object to be dyed without being in contact with the intermediate recording medium, and heated in a state where the gap between the toner adhesion surface of the intermediate recording medium and the surface of the object to be dyed was 1 μm to 150 μm. In this case, the sublimating dye in the toner adhering to the intermediate recording medium can be sublimated and transferred to the object to be dyed to obtain a dyed product, the dyeing density of the dyed product is sufficient, and the dyed image has high transparency and excellent quality. Moreover, it was possible to obtain a dyed product that did not impair the feel of the touch, and it was possible to avoid adhesion between the intermediate recording medium and the dyed product.

On the other hand, in Comparative Example 1 in which the intermediate recording medium and the object to be dyed are in close contact with each other, and Comparative Example 2 in which the metal foil of 0.1 μm is used, the adhesion between the intermediate recording medium and the dyed object is severe, and the measurement accuracy of the stained image is high. Since it became worse, it is described as a reference value. Further, in Comparative Example 3 in which a gap of 250 μm was opened with a height gauge, the image became unclear due to the large gap, and the image of 0.2 mm thin lines was diffused and could not be measured accurately. It was diffused to 6 mm. In Comparative Example 4 in which the projected area ratio of the filter medium used as the spacer exceeded 99%, a sufficient dyeing concentration could not be obtained because the sublimation dye was transmitted and the sublimation transfer path was insufficient, and the dyeing concentration was 0.2 mm. The thin line image was also blurred, which was not a practical result.

Claims (6)

After forming an image on an intermediate recording medium using a dry toner containing a sublimation dye by an electrophotographic method, the intermediate recording medium is opposed to the object to be dyed without being in contact with the intermediate recording medium. The sublimation dye in the toner adhering to the intermediate recording medium is sublimated and transferred to the object to be dyed by heating with the gap between the toner adhering surface and the surface of the object to be dyed set to 1 μm to 150 μm. A method for producing a dyed product, which comprises obtaining a dyed product. The method for producing a dyed product according to claim 1, wherein a spacer is sandwiched between the intermediate recording medium and the dyed product to form the gap. The method for producing a dyed product according to claim 2, wherein the spacer is made of a filter material that allows the sublimation dye to permeate. In the method for producing a dyed product according to claim 3, the area A1 of the member forming the filter medium and the area A2 of the background obtained from an image obtained by photographing the filter medium placed on a predetermined background are obtained. A method for producing a dyed product, wherein the projected area ratio represented by the following formula (1) is 99% or less.
Projected area ratio (%) = A1 / (A1 + A2) Equation (1)
A1: Area of the member forming the filter medium (mm ² )
A2: Background area (mm ² ) The method for producing a dyed product according to claim 3 or 4, wherein the projected area ratio of the filter medium is 91% or less. The production of a dyed product according to any one of claims 3 to 5, wherein the filter medium is selected from Japanese paper, a non-woven fabric sheet, a cloth, and a heat-resistant resin mesh sheet. Method.

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