JP2014015685A - Sublimation transfer dyeing method, dyeing body, and toner used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sublimation transfer dyeing method in which a body to be dyed can be dyed by an electronic photographic method using a toner by high transfer efficiency; the body to be dyed that is dyed by the dyeing method by high efficiency; an intermediate record medium to which a toner used for the dyeing method is adhered; and the toner used for the dyeing method.SOLUTION: A sublimation transfer dyeing method is a dyeing method in which a toner is adhered to an intermediate record medium by an electronic photographic method, and a dye included in the toner adhered to the intermediate record medium is subjected to sublimation transfer to the body to be dyed, wherein an intermediate record medium in which a density is larger than 1.00 g/cmis used as the intermediate record medium, a toner that at least includes a styrene-acryl resin and a dispersion dye is used as the toner, and thereby the body to be dyed that is dyed by high transfer efficiency can be provided.

Description

  The present invention relates to a sublimation transfer dyeing method for dyeing an object to be dyed using an intermediate recording medium provided with a sublimation transfer toner, a dyed product obtained by the dyeing method, and a toner used in the dyeing method.

The dyeing method using the electrophotographic method for the hydrophobic fiber typified by polyester cloth or the hydrophobic resin typified by PET film can be roughly divided into two.
That is, a direct method in which a toner is directly applied to an object to be dyed, and then a dye contained in the toner is dyed on the object to be dyed by heat treatment; and an intermediate recording is performed after the toner is applied to an intermediate recording medium such as paper. A sublimation transfer method in which the toner application surface of the medium and the object to be dyed are superposed and then heat treatment is performed, and the dye contained in the toner is sublimated and transferred to the object to be dyed.

  Of these two methods, the sublimation transfer method is said to be suitable for dyeing for applications in which texture is important, such as clothing such as sports apparel. In addition, the dye in the toner used for the sublimation transfer method is an easily sublimation type that is excellent in sublimation transfer to hydrophobic fibers by heat treatment, among disperse dyes or oil-soluble dyes suitable for dyeing hydrophobic fibers. Are used.

When the sublimation transfer method is used in the electrophotographic system, it is possible to dye only the dye out of the plurality of components constituting the toner from the intermediate recording medium to the fiber. As a result, toner constituents other than the dye do not adhere to the dyed fabric, and are suitable for applications in which the texture of the fabric is important, such as clothing; interiors such as sheets and sofas; or beddings; In addition, it is possible to reduce the risk of occurrence of rash, eczema and the like due to toner constituents for people with sensitive skin quality.
In addition, the fact that processes such as washing and drying are not required greatly reduces the dyeing process; washing and drying lines and washing water treatment facilities that require high cost, large space and large operating energy There are also merits such as making unnecessary.
Therefore, the sublimation transfer method is regarded as an excellent staining method capable of staining even in a small space.

On the other hand, as a means for dyeing fibers by a sublimation transfer method, an ink jet method is generally used.
However, the ink-jet sublimation transfer dyeing has a problem that an organic solvent, which is one of the components constituting the ink, volatilizes due to heat when transferring the dye and contaminates the working environment.
On the other hand, in the electrophotographic system, there is no volatile component in the toner and the work environment is not contaminated; the fiber (or its structure) that can be dyed by the appearance of a photosensitive drum capable of outputting up to 900 mm width. In recent years, for example, the size of fabric etc. has become compatible with the sports apparel field; and the dyeing area per unit time is larger than that of the inkjet method (serial printing method); Gathered.

  Sublimation transfer dyeing using an electrophotographic method is disclosed, for example, in Patent Documents 1 to 5 below.

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

  The present invention relates to a sublimation transfer dyeing method capable of dyeing an object to be dyed with high transfer efficiency by an electrophotographic method using toner, an object to be dyed with high efficiency by the dyeing method, and a toner used in the dyeing method. It is an object of the present invention to provide an attached intermediate recording medium and a toner used in the dyeing method.

  As a result of intensive studies to solve the above problems, the present inventors have used the intermediate recording medium having a specific density, and a toner containing a specific resin and a disperse dye in combination to achieve the above problems. As a result, the present invention was completed. That is, the present invention relates to the following (1) to (15).

(1) A dyeing method in which toner is attached to an intermediate recording medium by an electrophotographic method, and a dye contained in the toner attached to the intermediate recording medium is sublimated and transferred to an object to be dyed. Sublimation transfer dyeing method using an intermediate recording medium having a particle size of greater than 1.00 g / cm ³ and using a toner containing at least a styrene-acrylic resin and a disperse dye as the toner.
(2) The intermediate recording medium is JIS P 0001: 1998 3. Classification f) Paper described in paper and board varieties and processed products; and JIS Z 0108: 2005 3. Classification b) Packaging material 1) Cellophane described in relation to paper and paperboard; Sublimation transfer dyeing method according to (1) above, which is paper selected from the group consisting of:
(3) The sublimation transfer dyeing method according to (1) or (2), wherein the intermediate recording medium is a paper containing cellulose.
(4) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is tracing paper.
(5) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is glassine.
(6) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is sulfate paper.
(7) The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is paraffin paper or wax paper.
(8) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is oil-resistant paper.
(9) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is capacitor paper.
(10) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is varnish paper.
(11) The sublimation transfer dyeing method according to any one of (1) to (3), wherein the intermediate recording medium is bond paper.
(12) The object to be dyed is selected from hydrophobic fibers or structures thereof, films and sheets made of a hydrophobic resin, cloth coated with a hydrophobic resin, glass, metal, or pottery. Sublimation transfer dyeing method.
(13) An article to be stained dyed by the sublimation transfer dyeing method according to (1) or (12).
(14) An intermediate recording medium for use in the sublimation transfer dyeing method according to (1) above, wherein the toner is attached by an electrophotographic method and the density is greater than 1.00 g / cm ³ .
(15) A toner containing at least a styrene-acrylic resin and a disperse dye, which is used in the sublimation transfer dyeing method according to (1).

  According to the present invention, there is provided a sublimation transfer dyeing method capable of dyeing an object to be dyed with high transfer efficiency by an electrophotographic method using toner, an object to be dyed with high efficiency by the dyeing method, and a toner used in the dyeing method. The attached intermediate recording medium and the toner used in the dyeing method could be provided.

As the intermediate recording medium, any intermediate recording medium having a density greater than 1.00 g / cm ³ can be used. Among them, “Paper / paperboard and pulp terms” [JIS P 0001: 1998 (confirmed in 2008, revised on March 20, 1998, published by the Japanese Standards Association)], pages 28-47. Paper and paperboard types and processed products described in “3. Classification f) Paper and board types and processed products” (Nos. 6001 to 6284, provided that “oil resistance” No. 6235, “flute, corrugated”, 6273 “pulp molding”, 6276 “carbon paper”, 6277 “multi-copy foam paper”, 6278 “back carbon foam paper”); and cellophane (hereinafter referred to as “paper / paperboard varieties and processed products”; and Cellophane "is referred to as" paper etc. ").
Cellophane is described in “Packaging terminology“ Glossary of terms for packaging ”[JIS Z 0108: 2005 (confirmed in 2009, revised on June 20, 2005, published by the Japanese Standards Association)]. Classification b) Packaging material 1) It means cellophane described in the number 2009 related to paper and paperboard.
Some of the papers described above do not contain cellulose, and are not normally classified as paper. However, in the present specification, such paper and the like are also included in the meaning of paper.

Examples of the paper include ivory, asphalt paper, art paper, colored board paper, color fine paper, inkjet paper, printing paper, printing paper, printing paper A, printing paper B, printing paper C, printing paper D. , Indian paper, thin-leaf printing paper, thin-leaf Japanese paper, back carbon paper, air mail paper, sanitary paper, embossed paper, OCR paper, offset paper, cardboard, chemical fiber paper, processed paper, art paper, pattern paper, one piece and kraft paper , Wallpaper base paper, paper thread base paper, paper string base paper, pressure-sensitive copying paper, photosensitive paper, thermal paper, crust paper, paperboard for cans, yellow paperboard, fake leather paper, ticket paper, functional paper, cast coated paper, Kyoto flower paper, Office paper, metallized paper, metal foil, glassine, gravure paper, kraft paper, craft stretch paper, craft ball, crepe paper, lightweight coated paper, insulating paper for cables, base paper for decorative boards, Base paper, Kent paper, Abrasive base paper, Synthetic paper, Synthetic fiber paper, Coated paper, Capacitor paper, Hybrid paper, Additional paper, Exposed kraft paper, Diazo photosensitive paper, Paper tube base paper, Magnetic recording paper, Paperboard board, Dictionary paper, Light-shielding paper, double kraft paper for heavy bags, pure white roll paper, securities paper, shoji paper, high-quality paper, information paper, food container base paper, book paper, calligraphy paper, white paperboard, white ball, newspaper web, blotting paper, water-soluble Paper, drawing paper, lined kraft paper, square eye paper, speaker cone paper, electrostatic recording paper, physiological paper / cotton paper, laminated base paper, gypsum board base paper, adhesive base paper, semi-quality paper, cement bag paper , Ceramic paper, solid fiber board, tarfelt base paper, tarpaulin paper, alkali resistant paper, fireproof paper, acid resistant paper, oil resistant paper, towel paper, sandpaper, corrugated paper, corrugated paper, map paper, chipboard , Medium quality paper, neutral paper, dust paper, matte art paper, tea bag paper, tissue paper, electrical insulation paper, classic paper, paste paper, transfer paper, toilet paper, statistics card paper, photocopier paper, coating Printing paper, coated paper base, bird cub, tracing paper, medium base paper, napkin base paper, flame retardant paper, NIP paper, tag paper, adhesive paper, carbonless paper, release paper, hatron paper, baryta paper, paraffin paper Waxed paper, vulcanized fiber, semi-paper, PPC paper, writing paper, finely coated printing paper, form paper, continuous slip paper, copy paper, pressboard, moisture-proof paper, service paper, waterproof paper, rust-proof paper, packaging paper, bond Paper, Manila ball, Mino paper, Shoin paper, Milk carton base paper, Imitation paper, Oil paper, Yoshino paper, Rice paper, Cigarette paper, Liner liner, Sulfuric acid Paper, kraft paper, roofing base paper, filter paper, Japanese paper, varnish paper, one-pump, lightweight paper, air-dried paper, wet strong paper, ashless paper, acid-free paper, finish paper or paperboard, double-layer paper or paperboard, three Laminated paper or paperboard, multilayer paper or paperboard, non-size paper, sized paper, woven paper, wood grain paper or paperboard, machine finished paper or paperboard, machine glossy finished paper or paperboard, plate glossy finished paper or paperboard, friction glossy finished paper or Paperboard, calendered paper or paperboard, super calendered paper, lamin (paper or paperboard), single-sided colored paper or paperboard, double-sided colored paper or paperboard, twin wire paper or paperboard, rug paper, all rug paper, mechanical pulp paper or paperboard , Mixed straw pulp paper or paperboard, water finish paper or paperboard, chip ball, laminated chip ball, millboard, high gloss millboard, homogeneous paperboard, mechanical pulp board , Brown mechanical pulp board, brown mixed pulp board, artificial leather board, asbestos board, felt board, tar brown paper, water leaf paper, surface size paper, press pan, press paper, wrinkled finish paper, bonded ivory, blade coating Technical paper, roll coated paper, gravure coated paper, size press coated paper, brush coated paper, air knife coated paper, extrusion coated paper, dip coated paper, curtain coated paper, hot melt coated paper, Solvent coated paper, emulsion coated paper, bubble coated paper, imitation art paper, Bible paper, poster paper, packaging tissue, base paper, carbon base paper, diazo photosensitive paper base, photographic paper base, frozen food base paper: Direct contact paper, frozen food paper base: non-contact paper, safety paper, banknote paper, insulation paper or paperboard, laminated insulation paper, electrical insulation for cables , Shoeboard paper, woven paper tube paper, stencil paper or paperboard, squeeze paperboard, bookbinding paperboard, paperboard for clothes box, paper-type paper, recording paper, craft liner, certified liner, craft tension liner, waste paper liner, Envelope paper, folding box board, coated folding box board, bleached pulp lined folding box board, typewriter paper, photocopied paper, spirit copy paper, calendar roll paper, corrugated paper, corrugated paper, corrugated paper, Double-layer tar paper, Reinforced double-layer tar paper, Upholstery paper or paperboard, Cloth paper or paperboard, Reinforcement paper or Reinforcement paperboard, Carton compact, Overlay, Wet crepe, Index card, Carbonless foam paper, Envelope , Postcards, postcards with pictures, postal letters, postal letters with pictures, etc .; and cellophanes;
Any of these papers can be used as an intermediate recording medium as long as the density is greater than 1.00 g / cm ³ .
As will be described later, when performing sublimation transfer, heat treatment is usually performed at about 190 ° C. to 210 ° C. Therefore, among papers having a density greater than 1.00 g / cm ^3, those that are stable during the heat treatment are preferable.

The above-mentioned density measurement method is measured in accordance with “Paper and paperboard—Thickness and density test method [JIS P 8118: 1998 (2010 confirmed, revised on November 20, 1998, published by the Japanese Standards Association)]”. can do.
As the intermediate recording medium having a density higher than 1.00 g / cm ^{3, the} above-mentioned paper is preferably exemplified. Moreover, the paper containing a cellulose is more preferable. Among them, tracing paper; glassine; sulfate paper; paraffin paper / wax paper; oil-resistant paper; capacitor paper; varnish paper; bond paper; However, even these papers have a density of 1.00 g / cm ³ or less, and therefore the density is preferably measured according to the above method.
Usually greater than 1.00 g / cm ³ as the density of the intermediate recording medium, preferably greater 2.00 g / cm ³ or less than 1.00 g / cm ^3, more preferably greater than 1.00g / cm ³ 1.80g / cm ³ or less, more preferably 1.01 g / cm ³ or more 1.70 g / cm ³ or less, and if the preferably 1.02 g / cm ³ or more 1.60 g / cm ³ or less, particularly preferably 1.03 g / cm ³ or more and 1.59 g / cm ³ or less.

The tracing paper may be further specially processed for the purpose of improving strength and transparency. Examples of such processing include a method of treating tracing paper with fats, oils, resins or waxes; a method of performing mechanical treatment at the stage of preparing the stock; and the like.
Tracing paper subjected to these processes is also preferable as an intermediate recording medium.

The glassine generally has a high transparency, but is made opaque by adding a filler, and any of them is useful as an intermediate recording medium. In general, glassine is often used for food packaging, container lining, and the like because it is required to have no pinholes and good oil resistance.
Any such glassine is preferred as an intermediate recording medium.

The sulfuric acid paper has high resistance to penetration of organic liquids, especially oil paper and grease; it also has the property of being resistant to disaggregation by boiling water, tasteless, odorless and oil resistant. It is often used for packaging of butter, cheese, meat, etc. for reasons such as being water resistant.
Such sulfate paper is also preferable as an intermediate recording medium.

  The paraffin paper / wax paper is manufactured by coating or impregnating glassine, imitation paper, kraft paper or the like with a coating agent mainly composed of paraffin. Any such paraffin paper or wax paper is preferable as the intermediate recording medium.

  “Oil-resistant paper”, a generic term for oil-resistant paper, is a paper that is made using highly refined chemical pulp, and is chemically treated and / or coated so that it is resistant to oils and fats. Paper. Any such oil-resistant paper is preferable as an intermediate recording medium for sublimation transfer printing.

The capacitor paper is a paper used as a dielectric material sandwiched between capacitor paperboards, and is manufactured using kraft pulp or the like as a main raw material. The performance is required to have no pinholes; to be chemically neutral; to contain as far as possible no electrically harmful substances, particularly conductive fine particles;
Any such capacitor paper is preferred as an intermediate recording medium.

  The varnish paper is an electrically insulating paper in which a resin is dissolved in a dry oil or a boil oil, diluted with turpentine oil or petroleum, and impregnated into a base paper. Any such varnish paper is preferred as the intermediate recording medium.

  The above bond paper is a hard cardboard made by thoroughly beating rag pulp, bleached chemical pulp, etc., and using the strength size (bleeding prevention agent), and has good printability, good writability and durability. Used as high quality printing paper for securities. Any such bond paper is preferred as an intermediate recording medium.

  The toner contains at least a styrene-acrylic resin and a disperse dye.

Although it does not specifically limit as said styrene-acrylic resin, For example, resin obtained by superposing | polymerizing two types of monomers, a styrene-type monomer and a monofunctional (meth) acrylic-type monomer, is mentioned. . “(Meth) acryl” means “acryl” and / or “methacryl”.

  The styrene monomer is not particularly limited, and examples thereof include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, 4, α-dimethyl styrene, and p-ethyl styrene. 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-pentylstyrene, pn-hexylstyrene, pn-heptyl Examples include styrene, pn-octyl styrene, pn-nonyl styrene, pn-decanyl styrene, pn-dodecyl styrene, p-phenyl styrene, 3,4-dicyclosyl styrene, and the like. Of these, styrene is preferred. These styrenic monomers may be used alone or in combination of two or more.

  The monofunctional (meth) acrylic monomer is not particularly limited. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, Acrylic monomers such as n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octadecyl acrylate, methyl α-chloroacrylate, ethyl α-chloroacrylate; methacrylic acid, methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-cyclohexyl methacrylate, methacrylate And methacrylic monomers such as n-dodecyl sulfate, n-tridecyl methacrylate, and n-octadecyl methacrylate; Among these, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacryl Isobutyl acid and tert-butyl methacrylate are preferable, and n-butyl acrylate and n-butyl methacrylate are particularly preferable. These monofunctional (meth) acrylic monomers may be used alone or in combination of two or more.

  The styrene-acrylic resin may be a resin obtained by polymerizing three types of monomers by further containing a polyfunctional vinyl monomer in addition to the two types of monomers. The polyfunctional vinyl monomer is not particularly limited as long as it is a compound having two or more ethylenically unsaturated groups in one molecule. Specific examples thereof include, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di Polyethylene glycol (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, di (meth) acrylic acid bisphenol A derivative, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like. These polyfunctional vinyl monomers may be used alone or in combination of two or more. Among these, trimethylolpropane tri (meth) acrylate is preferable.

Content of the structural unit corresponding to each said monomer in the total mass of a styrene-acrylic resin is not specifically limited.
However, in the total mass of the styrene-acrylic resin, the content of the structural unit corresponding to the styrene monomer is usually 50 to 95%, preferably 60 to 90%, more preferably 70 to 90% on a mass basis. 90%. By setting this content, the fixability to the intermediate recording medium tends to be good. In the present specification, unless otherwise specified, both “%” and “parts” are described on a mass basis.
Similarly, the content of the structural unit corresponding to the monofunctional (meth) acrylic monomer is usually 5 to 50%, preferably 10 to 40%, more preferably 10 to 30%. By setting this content, in addition to the fixability to the intermediate recording medium, the storage stability tends to be improved.
Further, when the polyfunctional vinyl monomer is further contained, the content of the structural unit corresponding to the polyfunctional vinyl monomer is also usually 0.05 to 3%, preferably 0.1 to 2. %, More preferably 0.3 to 1%. When the polyfunctional vinyl monomer is further contained, the content of the styrene monomer and / or the monofunctional (meth) acrylic monomer may be adjusted according to the content.

The styrene-acrylic resin is necessary in addition to the three types of monomers, a styrene monomer, a monofunctional (meth) acrylic monomer, and optionally a polyfunctional vinyl monomer. Depending on the case, a resin obtained by adding other vinyl monomers and polymerizing them may be used.
Other vinyl monomers are not particularly limited, but examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; maleic acid Examples thereof include vinyl monomers containing carboxy groups such as monomethyl, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate and monobutyl fumarate;

  As said styrene-acrylic resin, resin obtained by superposing | polymerizing two types of monomers, a styrene-type monomer and a monofunctional (meth) acrylic-type monomer, is preferable.

The number average molecular weight (Mn) by GPC analysis of the THF (tetrahydrofuran) soluble component (hereinafter referred to as “THF soluble component”) of the styrene-acrylic resin is not particularly limited, but is usually 1,000 to 20,000. , Preferably 2,000 to 10,000, more preferably 3,000 to 6,000.
Moreover, the mass average molecular weight (Mw) by GPC of the THF-soluble component of the styrene-acrylic resin is not particularly limited, but is usually 10,000 to 300,000, preferably 12,000 to 280,000, more preferably. Is 14,000 to 270,000.

The GPC analysis of the THF-soluble component was analyzed using a high-speed GPC apparatus (HLC-8320GPC EcoSEC, manufactured by Tosoh Corporation) using a 1.0% THF solution of styrene-acrylic resin as a sample solution. The column used for the analysis was composed of one TSKgel / SuperHZ1000 column (manufactured by Tosoh Corp.), one TSKgel / SuperHZ2000 column (manufactured by Tosoh Corp.), and two columns of TSKgel / SuperMultipore HZ-H (manufactured by Tosoh Corp.). used.

  The acid value of the styrene-acrylic resin is not particularly limited, but is usually 0.5 to 40 mgKOH / g, preferably 1 to 30 mgKOH / g, and more preferably 1 to 10 mgKOH / g.

The glass transition temperature (Tg) of the toner is not particularly limited, but is usually 40 to 75 ° C, preferably 40 to 70 ° C, and more preferably 50 to 65 ° C.
The glass transition temperature (Tg) was determined by packing 3 mg of toner in an aluminum cell and using a differential scanning calorimeter (DSC 6220, manufactured by Seiko Instruments Inc.), a measurement temperature of 20 ° C. (measurement start temperature) to 200 ° C. (Measurement end temperature), measured at a temperature elevation rate of 6 ° C./min.

The softening point (T4) of the toner is not particularly limited, but is usually 90 to 160 ° C, preferably 100 to 150 ° C, more preferably 110 to 145 ° C.
In addition, a softening point (T4) is a pore diameter 1.0mm x pore length 1 about 1.0g of samples using a constant load extrusion capillary type rheometer (manufactured by Shimadzu Corporation, flow tester CFT-500D). Using a 0.0 mm die, the temperature was measured at a rate of temperature increase of 3.0 ° C./min and a load of 30 kg, and the plunger descending amount was 4 mm.

  The method for producing the styrene-acrylic resin is not particularly limited, and any known method can be used. As an example, for example, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used. Moreover, you may mix the resin each manufactured by these several polymerization methods. Among these, the suspension polymerization method is preferable.

  Some of the styrene-acrylic resins are available as commercial products. For example, Almatex CPR-100, CPR-250, CPR-390, CPR-400, etc. manufactured by Mitsui Chemicals, Inc. may be mentioned. Among these, CPR-390 is preferable.

The disperse dye is not particularly limited, but a dye having sublimation transfer suitability is preferable.
“Dye suitable for sublimation transfer” means “Test method for fastness of dyeing to dry heat treatment [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by the Japanese Standards Association)” The heat-sensitive test (Method C) stain (polyester) test result usually means a dye having a grade of 3-4 or less, preferably a grade 3 or less. Among such dyes, examples of known dyes include the following dyes.
Examples of yellow dyes include C.I. I. Disperse yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; 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;
Any of the above dyes may be used alone or in combination of two or more.

It is also preferable to blend a plurality of dyes to obtain a completely different hue from the original dye, such as black. In this case, for example, a black dye can be obtained by appropriately blending a yellow dye and a red dye mainly containing a blue dye.
Furthermore, for example, a plurality of dyes may be blended for the purpose of finely adjusting a color tone such as blue, yellow, orange, red, violet, or black to a more preferable color tone; or for obtaining an intermediate color.

The toner may further contain a wax, a charge control agent, an external additive and the like as necessary.

There is no restriction | limiting in particular as said wax, It can select suitably from well-known waxes. Among them, a low melting point wax having a melting point of 50 to 120 ° C. is preferable. The low melting point wax, when dispersed with the styrene-acrylic resin, effectively acts as a mold release agent between the fixing roller and the toner interface, so that it is oil-less (for example, oil like oil on the fixing roller). The hot offset resistance is good even when the mold release agent is not applied.
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 and micro wax And natural waxes such as petroleum waxes such as crystallin and 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 hydrocarbons; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n-lauryl Polyacrylate homopolymer or copolymer such as methacrylate (for example, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. may be used as wax. good.
Any of the aforementioned waxes may be used alone or in combination of two or more.

The melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and / or low-temperature fixability may not be obtained.

  Some of the waxes are commercially available. For example, carnauba wax preferably includes Carnauba wax C1 manufactured by Kato Yoko Co., Ltd., and montan wax includes Licowax KP manufactured by Clariant.

There is no restriction | limiting in particular as said 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 aforementioned charge control agents may be used alone or in combination of two or more.

Some of the charge control agents are available as commercial products. For example, Nigrosine dye Bontron ^RTM 03, quaternary ammonium salt Bontron ^RTM P-51, metal-containing azo dye Bontron ^RTM S-34, oxynaphthoic acid metal complex Bontron ^RTM E-82, salicylic acid metal complex Bontron ^RTM E-84, phenol-based condensate Bontron ^RTM E-89 (above, Orient Chemical Industries, Ltd.); quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industries, Ltd.) Quaternary ammonium salt copy charge ^RTM PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge ^RTM NEG VP2036, copy charge ^RTM NX VP434 (above, Hoechst); LRA -901, LR-147, a boron complex (Japan Carri Company 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.

The external additive can be used for the purpose of imparting fluidity, developability, chargeability and the like to the toner particles. There is no restriction | limiting in particular as an external additive, It can select suitably from well-known external additives.
Specific examples of the external additive include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite Diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
Any of the aforementioned external additives may be used alone or in combination of two or more.

The primary additive has a primary particle size of preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the external additive according to the BET method is preferably 20 to 500 m ² / g.

Some of the external additives are available as commercial products. For example, silica produced by Nippon Aerosil Co., Ltd. ^{AEROSIL RTM R812, AEROSIL RTM RX50,} AEROXIDE RTM Alu C 805 , etc. of the alumina; acid value of titanium manufactured by Nippon Aerosil Co., Ltd. _{^{AEROXIDE RTM TiO 2 T805, AEROXIDE RTM}} TiO 2 NKT90 Etc .; Examples of strontium titanate include ST, CT, HST-1, HPST-1, and HPST-2 manufactured by Fuji Titanium.

The content of the dye contained in the toner is not particularly limited and can be appropriately selected according to the purpose. The standard of the content of the dye is usually 1 to 40%, preferably 2 to 35% with respect to the total mass of the toner.
When the content of the dye is less than 1%, the dyeing density is lowered, and when it exceeds 40%, the dye is poorly dispersed in the toner, and the electrical characteristics of the toner may be lowered.

The content of the resin contained in the toner is not particularly limited and can be appropriately selected according to the purpose. The standard for the resin content is usually 60 to 99%, preferably 65 to 98%, based on the total mass of the toner.
When the resin content is less than 60%, poor dispersion of the dye in the toner occurs, which may cause a decrease in toner electrical characteristics. When the resin content exceeds 99%, a decrease in dyeing density is observed.

There is no restriction | limiting in particular in content of the wax contained in the said toner, According to the objective, it can select suitably. 0.1 to 20% is preferable, and 0.5 to 10% is more preferable.
When the wax content is less than 0.1%, offset to the fixing roller occurs, and when it exceeds 20%, fixing failure to the intermediate recording medium is observed.

  The content of the charge control agent contained in the toner is not particularly limited and can be appropriately selected. The content varies depending on the kind of the resin, the presence / absence of an additive, a dispersion method, and the like, and it is difficult to define it in general. However, when the charge control agent is contained, the content is usually 0.1 to 10%, preferably 0.2 to 5%, based on the total mass of the resin contained in the toner.

  When the content of the charge control agent is less than 0.1%, the charge controllability may not be obtained. When the content exceeds 10%, the chargeability of the toner becomes too large, and the effect of the charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in toner fluidity and a decrease in image density.

  The content of the external additive contained in the toner is not particularly limited and can be appropriately selected. As a guideline for the content of the external additive, it is usually 0.01 to 5.0%, preferably 0. It is 05 to 4.9%.

A method for producing the toner will be described.
As a toner manufacturing method, in addition to a pulverization method prepared through kneading, pulverization, and classification processes, a polymerized toner is polymerized, and toner particles are formed while simultaneously controlling the shape and size. Methods (for example, an emulsion polymerization method, a dissolution suspension method, an emulsion association method, a polyester stretching method, etc.) can be applied. The pulverization method is preferable in that the production can be performed at high speed. The toner production method by the pulverization method generally includes the following three steps of production steps 1 to 3.

"Manufacturing process 1"
A step of obtaining a dye-resin mixture by mixing a dye, a resin, and, if necessary, a charge control agent, wax and the like with a mixer such as a Henschel mixer.
"Manufacturing process 2"
A step of melt-kneading the dye-resin mixture with a closed kneader; or a monoaxial or biaxial extruder; etc., and cooling to obtain a resin composition.
"Manufacturing process 3"
The resin composition is coarsely pulverized with a hammer mill or the like, then finely pulverized with a jet mill or the like, and classified as needed to obtain a target particle size distribution using a cyclone to obtain a toner (toner particle). Process.

  Also included is “Manufacturing Step 4” in which the external additive is added to the toner obtained in the above-mentioned Manufacturing Step 3 as necessary and mixed with a Henschel mixer or the like to obtain a toner with the external additive added. This is also preferably done.

The toner produced as described above can be used as a magnetic or non-magnetic one-component developer, but can also be mixed with a carrier and used as a two-component developer.
As the carrier, magnetic particles made of a known material such as metals such as iron, ferrite and magnetite; alloys of these metals with metals such as aluminum and lead; and the like can be used, and ferrite particles are particularly preferable. Further, a coat carrier in which the surface of magnetic particles is coated with a coating agent such as a binder resin, a binder type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.

In an electrophotographic system using toner, an image is generally printed on an intermediate recording medium by the following operations (1) to (3).
(1) An electrostatic latent image formed by exposure on a latent image carrier such as a photosensitive drum is developed with a developer using toner to form a toner image.
(2) The obtained toner image is transferred to an intermediate recording medium such as paper by a transfer member, thereby forming a toner image on the intermediate recording medium.
(3) The obtained intermediate recording medium is heated and pressurized by a fixing device, and the toner image formed on the intermediate recording medium is fixed on the intermediate recording medium. Thereby, the printing of the image on the intermediate recording medium is completed.

The fixing device is generally not limited in particular, although the sheet is sandwiched between a pair of rollers provided with a heater and heated and pressurized while the sheet is conveyed by rotation of the roller. The surface temperature of the roller is usually heated to about 80 to 170 ° C. by a heater.
The fixing device may have a cleaning function. Examples of the cleaning method include a method of cleaning by supplying silicone oil to the roller; a method of cleaning the roller with a pad, roller, web, etc. impregnated with silicone oil;

  As a sublimation transfer dyeing method, for example, a toner image is formed on the intermediate recording medium by, for example, a known electrophotographic method, and a toner image is formed by superimposing the toner adhesion surface of the intermediate recording medium and the object to be dyed. A dyeing method in which a sublimable dye in a toner is transferred and dyed from an intermediate recording medium to an object to be dyed, usually by heat treatment at about 190 to 210 ° C., and the toner image on the intermediate recording medium is sublimated and transferred to the object to be dyed. Is mentioned.

  Examples of materials to be dyed include hydrophobic fibers typified by polyester (or cloths that are structures thereof); or films and sheets made of hydrophobic resins typified by PET films and PET sheets; hydrophobic resins Are coated with fabric, glass, metal, earthenware and the like.

An intermediate recording medium used in the sublimation transfer dyeing method and having a density greater than 1.00 g / cm ³ to which toner is attached by electrophotography is also included in the scope of the present invention. As described above, the density of the intermediate recording medium means the density of the intermediate recording medium before the toner is attached.

By using the toner and the sublimation transfer dyeing method, the sublimation dye in the toner attached to the intermediate recording medium can be sublimated and transferred to the object to be dyed with high transfer efficiency. It became possible to get. As a result, the dye in the toner can be used efficiently, and the burden on the environment can be reduced.
Further, since the amount of toner required for dyeing the object to be dyed is small, the cost for dyeing can be reduced, and a dyeing method having excellent cost merit can be provided.
Furthermore, since the amount of dye remaining on the intermediate recording medium after sublimation transfer is extremely small, the intermediate recording medium after sublimation transfer dyeing, which cannot be deinked normally and discarded by incineration or the like, is recycled paper. The possibility of being recyclable, etc. arises and can be expected as an environmentally friendly dyeing method.

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, “parts” and “%” are based on mass unless otherwise specified.
In the examples, the average particle size was measured using a precision particle size distribution analyzer “Multisizer ^RTM 3 (manufactured by Beckman Coulter, Inc.)”.

[Toner Preparation Example 1]
(Process 1)
Almatex CPR-390 (100 parts, Tg: 60 ° C., T4: 134 ° C.), Kaya Set Red B (manufactured by Nippon Kayaku Co., Ltd., CI Disper Thread 60: 10 parts), manufactured by Mitsui Chemicals, Inc. Bontron ^RTM E-84 (1 part) and Licowax ^RTM KP (4 parts) were premixed with a Henschel mixer at a rotational speed of 30 m / second for 10 minutes, and then melt-kneaded with a twin screw extruder. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier to obtain particles having an average particle diameter of 9.4 μm.

(Process 2)
The particles (100 parts) obtained in the toner preparation example 1 (step 1), AEROSIL ^RTM R812 (1 part), and AEROSIL ^RTM RX50 (1 part) are placed in a Henschel mixer and stirred for 10 minutes at a rotation speed of 30 m / sec. As a result, magenta toner 1 was obtained.

[Toner Preparation Example 2 (Preparation of Comparative Toner)]
(Process 1)
ACT-6217 manufactured by DIC Corporation (100 parts, Tg: 64 ° C., T4: 130 ° C.), Kaya Set Red B (manufactured by Nippon Kayaku Co., Ltd., CI Disper Thread 60: 10 parts), Bontron ^RTM E -84 (1 part) and Licowax ^RTM KP (4 parts) were placed in a Henschel mixer, premixed for 10 minutes at a rotational speed of 30 m / sec, and then melt-kneaded by a twin screw extruder. The obtained melt-kneaded product was pulverized and classified using a pulverizer / classifier, thereby obtaining particles having an average particle diameter of 9.8 μm.

(Process 2)
The particles (100 parts) obtained in the toner preparation example 2 (step 1), AEROSIL ^RTM R812 (1 part), and AEROSIL ^RTM RX50 (1 part) are placed in a Henschel mixer and stirred for 10 minutes at a rotation speed of 30 m / sec. As a result, a comparative magenta toner 2 was obtained.
The resin (ACT-6217) contained in the obtained toner is a polyester resin and is not included in the present invention.

[Setting of printing machine and printing conditions for attaching toner to intermediate recording medium]
(Printer settings)
The genuine toner inside the toner cartridge (Magenta) of the electrophotographic printer “Satera ^RTM LBP5910” (manufactured by Canon Inc.) was extracted, and the magenta toner 1 of the present invention obtained in Preparation Example 1 was inserted.
Next, using Adobe Systems' image processing software "Adobe ^RTM Photoshop 7.0", create a table of document size: A4, resolution: 600 pixels / inch, mode: RGB color, and print output of magenta toner Image data of R: 255, G: 0, and B: 255 (magenta toner 100% output A4 solid pattern) is created so that 100% is 100%. The printing conditions shown in Table 1 below are the 100% output A4 solid pattern. The printer was set to print 200 copies and replace the genuine toner remaining in the drum cartridge with the magenta toner 1 of the present invention, and attach the magenta toner 1 of the present invention to the intermediate recording medium.
Further, a printing machine for setting the comparative magenta toner 2 on the intermediate recording medium was set in the same manner as described above except that the comparative magenta toner 2 was used instead of the magenta toner 1 of the present invention.

(Setting printing conditions)
Using the image processing software “Adobe Photoshop 7.0” (manufactured by Adobe Systems Co., Ltd.), a table of document size: A4, resolution: 600 pixels / inch, mode: RGB color is created, and the conditions described in Table 2 below are set. The RGB color mixture data was input to create a test pattern from 0% to 100% in print output in 5% increments, and the printing conditions were set.

[Example 1]
As an intermediate recording medium, using the printing machine set as described above on tracing paper having a density of 1.09 g / cm ³ (manufactured by KOKUYO, tracing paper A4 thick mouth 75 g / m ² ), The printing was performed under the printing conditions, and an intermediate recording medium (tracing paper) with magenta toner 1 adhered thereto was obtained.
After superposing the toner adhesion surface of the obtained intermediate recording medium and satin (weight per unit area: 90 g / m ² ) composed of 100% polyester fiber, a heat press machine (transfer press machine TP- manufactured by Taiyo Seiki Co., Ltd.) The satin dyed material dyed by the sublimation transfer dyeing method of the present invention was obtained by heat treatment under the conditions of 195 ° C. × 60 seconds using 600A2).

[Comparative Example 1]
An intermediate recording medium (tracing paper) to which a comparative magenta toner 2 is adhered and a satin dyeing for comparison are prepared in the same manner as in Example 1 except that the magenta toner 2 is used instead of the magenta toner 1. Obtained.

[Comparative Example 2]
As an intermediate recording medium, instead of the tracing paper used in Example 1, a PPC paper (TPPAPER A4, manufactured by Ricoh Co., Ltd.) having a density of 0.77 g / cm ³ was used in the same manner as in Example 1. Thus, an intermediate recording medium (PPC paper) on which magenta toner 1 was adhered and a satin dyeing for comparison were obtained.

[Comparative Example 3]
As an intermediate recording medium, PPC paper (TPPAPER A4, manufactured by Ricoh Co., Ltd.) having a density of 0.77 g / cm ³ is used instead of the tracing paper used in Example 1, and in addition to magenta toner 1. In the same manner as in Example 1 except that magenta toner 2 was used, an intermediate recording medium (PPC paper) on which magenta toner 2 was adhered and a satin dyeing for comparison were obtained.

[(A) Sublimation transfer efficiency test]
For each of the intermediate recording media obtained in Example 1 and Comparative Examples 1 to 3, a portion corresponding to each print output% of the intermediate recording medium before and after the sublimation transfer by heat treatment was spectrophotometer “Spectroeye (manufactured by Gretag Macbeth Co., Ltd.). ) ”Was used to measure the color density of the magenta color. The results are shown in Table 3 below.
For each of Example 1 and each comparative example, the sublimation transfer efficiency was calculated from the concentration of the dye adhered to the intermediate recording medium before and after transfer according to the following equation.
Sublimation transfer efficiency = (dye density after transfer−dye density before transfer) / (dye density before transfer) × 100%
Note that the print output of 0% is a measured value of the intermediate recording medium itself before the toner is adhered, and thus the sublimation transfer efficiency was not calculated. The calculation results are shown in Table 4 below.

As is apparent from Tables 3 and 4 and particularly Table 4, the sublimation transfer efficiency of the examples was significantly higher than that of each of the comparative examples, and it was found that the dye in the toner can be transferred to the object to be dyed with extremely high efficiency. .
Further, the staining density of the object to be dyed was measured with the above spectrophotometer. As a result, the to-be-dyed material of Example 1 had an extremely high dyeing density of 1.26 at the 100% printed output.
Furthermore, the gradation in the portion where the print output is as low as 5% to 45% is particularly clear, and a higher dye density than in each comparative example was obtained.
From the above results, it was found that the dyeing method of the present invention has practically sufficient performance.

  The sublimation transfer dyeing method of the present invention is an environmentally friendly dyeing method because the dye contained in the toner can be sublimated and transferred to an object to be dyed with high transfer efficiency. Therefore, it is extremely suitable as a sublimation transfer dyeing method in an electrophotographic system using toner.

Claims (15)

A dyeing method in which toner is attached to an intermediate recording medium by an electrophotographic method, and a dye contained in the toner attached to the intermediate recording medium is sublimated and transferred to an object to be dyed, and the density of the intermediate recording medium is 1. A sublimation transfer dyeing method using an intermediate recording medium of greater than 00 g / cm ³ and using a toner containing at least a styrene-acrylic resin and a disperse dye as the toner.   The intermediate recording medium is JIS P 0001: 1998 3. Classification f) Paper described in paper and board varieties and processed products; and JIS Z 0108: 2005 3. The sublimation transfer dyeing method according to claim 1, wherein the paper is selected from the group consisting of: b) packaging material 1) cellophane described in relation to paper and paperboard;   The sublimation transfer dyeing method according to claim 1 or 2, wherein the intermediate recording medium is a paper containing cellulose.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is tracing paper.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is glassine.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is sulfate paper.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is paraffin paper or wax paper.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is oil-resistant paper.   The sublimation transfer dyeing method according to claim 1, wherein the intermediate recording medium is capacitor paper.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is varnish paper.   The sublimation transfer dyeing method according to any one of claims 1 to 3, wherein the intermediate recording medium is bond paper.   2. The sublimation transfer dyeing method according to claim 1, wherein the material to be dyed is selected from hydrophobic fibers or structures thereof, films and sheets made of a hydrophobic resin, cloth coated with a hydrophobic resin, glass, metal, or earthenware. .   An article to be dyed by the sublimation transfer dyeing method according to claim 1 or 12. The intermediate recording medium for use in the sublimation transfer dyeing method according to claim 1, wherein the toner is attached by electrophotography and the density is higher than 1.00 g / cm ³ .   A toner containing at least a styrene-acrylic resin and a disperse dye used in the sublimation transfer dyeing method according to claim 1.