JP6810416B2 - Transfer printing method of polyester fiber - Google Patents

Description

The present invention relates to a transfer printing method for polyester fiber materials using a disperse dye.

As a method of applying a pattern or plain printing to a polyester fiber material with a disperse dye, screen printing, roller printing, and rotary screen printing using a color paste of a disperse dye are known and have been industrially practiced for a long time. However, these methods are inferior in design expressiveness, are not suitable for small lots and short delivery times because they require plate making, and because it is necessary to use a large amount of color glue and make excess color glue. Many problems have been pointed out, such as a large drainage load, many work processes and complexity, and the need for skill in delicate coloring and mold matching.

Therefore, a sublimation transfer method using a transfer paper in which an oil-based or water-based ink containing a sublimation type disperse dye (sublimation type disperse dye ink) is inkjet-printed on a sublimation transfer printing paper is described in Patent Document 1, Patent Document 2, and Patent Document 3. It is proposed in Patent Document 4 and is industrially implemented. However, these sublimation transfer methods have the following problems.

-Oil-based ink is a dangerous substance under the Fire Service Act, and it is necessary to pay attention to the prevention of fire and explosion, and also to the safety and health of human body and environmental pollution problems such as organic solvent poisoning.
-Since uniform dyeing property and reproducibility on polyester fibers are required, dyes having similar sublimation properties are required for each color, and the dyes that can be used are limited.
-Since the sublimation type disperse dye is a dye having a small molecular weight, it easily moves and diffuses by heat and jumps out from the inside of the fiber into the air, contaminating other fibers and white fields. For example, when the transfer temperature is high, the dye once dyed jumps out of the fiber material (fabric), so that there is a problem that the pattern is blurred and the transfer device and the environment are polluted. Therefore, a transfer temperature of 200 ° C. or lower is common, and Patent Document 4 discloses a method of lengthening the residence time (5 minutes) at a low temperature (140 ° C.). However, since this method has a problem in productivity, a condition of 30 seconds to 1 minute at a transfer temperature of 190 to 200 ° C. is usually adopted.
-Products dyed with sublimation-type disperse dyes have extremely low heat-resistant fastness, and their hue and other fastness are also limited, making them unsuitable for apparel as products to be processed.
-It is used in the sublimation transfer method and cannot be used for recycled paper because the sublimation dye remains on the paper peeled off after transfer and there are hydrangea spots.

On the other hand, when a non-sublimation type disperse dye is used instead of the sublimation type disperse dye and known sublimation transfer conditions are applied, good color development property cannot be obtained. That is, when transfer printing is performed on a known sublimation transfer printing paper using a transfer paper printed with a non-sublimation type disperse dye ink under known sublimation transfer conditions, the color development property is poor, and this method is of practical value. There is no.

As a method for solving these problems, in Patent Documents 5 and 6, an ink receiving layer is formed on a paper pattern, printed on the ink receiving layer with a disperse dye, and then a fiber material of the ink receiving layer. A method of sequentially performing a dye fixing process by dry transfer to a paper pattern, peeling of a paper pattern, steaming, or the like is disclosed. However, with this method, the cost of the release paper (base paper for transfer) is high, and the ink receiving layer may partially fall off if the humidity of the transfer factory or the storage conditions of the transfer printing paper are inappropriate. There are problems such as the ink receiving layer cannot be transferred 100% in the transfer process and defective products may occur, the dissociability of the paper is poor, it is difficult to recycle the paper, and the number of processes is large.

Further, Patent Document 7 describes a mixed paste obtained by adding a water-soluble synthetic binder, a natural paste, and an auxiliary agent to inexpensive commercially available paper to temporarily strengthen the adhesive force with the fiber material by heating and pressurizing. A method in which a transfer printing paper is produced by applying a liquid and drying to form an ink receiving layer and an adhesive layer, and a transfer paper having a dispersion dye ink printed on the transfer printing paper is attached to a fiber material to develop color. It is disclosed. This method is a processing method that has excellent points such as no pretreatment of fiber materials, but it requires a crimping process, a coloring process (dry heat treatment or steaming), a soaping process, etc., and the number of processes is large. There's a problem.

Further, Patent Document 8 (particularly, Example 4) describes dyes such as aqueous dispersions of non-sublimation type disperse dyes, viscosity modifiers, auxiliaries, monoalcohols having 1 to 5 carbon atoms, and water. A step of gravure-printing a water-based dye-based printing ink for gravure printing, which contains the above and has a viscosity thereof and the content of the monoalcohols within a specific range, on the printing paper to prepare a printing paper (transfer paper). , And a printing method including a step of adhering the transfer paper to a polyester fiber material to develop a transfer color is disclosed. This printing method is a printing method that can provide products of excellent quality with good reproducibility based on excellent economic efficiency and ecology, but as printing paper, water-soluble synthetic resin and natural glue are used for the base paper. Since an ink receiving layer made of a mixed paste containing an agent or the like is used, the transfer paper and the fiber material, which require a coating process for forming the ink receiving layer, are combined and crimped ( After pressurizing and / or heating), it is necessary to fix the dye by steaming or the like, and a cleaning step such as soaping is required to remove the ink receiving layer adhering to the fiber material. A printing method with a small number of steps has been desired.

Further, there is also known a direct method in which a disperse dye ink is printed on a dried fiber material (fabric) by applying a glue (pretreatment) to the fiber material with an inkjet printer. However, this method requires a pretreatment process, a printing process, a steaming process, and a soaping process for the fiber material, has a large number of processes and a large drainage load, has low productivity, and is inconvenient due to the pretreatment process and the printing process. There is a problem that the incidence of non-defective products tends to be high, that is, there is a problem in economic efficiency and quality stability.

In addition, the terms shown below for the paper used for printing in the present specification and claims represent the meanings shown below.
(1) Base paper: Paper not coated with glue as an ink receiving layer (2) Transfer printing paper (printing paper): Base paper coated with glue as an ink receiving layer (3) Transfer paper: Base paper or Paper after dye ink is applied to transfer printing paper

Japanese Unexamined Patent Publication No. 2003-313787 Japanese Unexamined Patent Publication No. 53-55221 Japanese Unexamined Patent Publication No. 2011-21133 JP-A-2002-292995 Japanese Patent No. 4058470 Japanese Unexamined Patent Publication No. 06-270596 Japanese Patent No. 4778124 Japanese Patent No. 5970588

As described above, a known sublimation transfer printing method (Patent Documents 1 to 4), a method of applying known sublimation transfer conditions to a non-sublimation type disperse dye, a known dry transfer method (Patent Documents 5 and 6), a direct method, Other known printing methods have product quality problems such as limited dyes, fastness, hue / color development, and quality stability, a large number of processes, and high raw material costs. Economic problems such as low productivity and high incidence of defective products, environmental problems such as polluting other fibers, environment and work environment, and heavy drainage load have been pointed out.

The present invention can stably produce a polyester fiber material having excellent quality such as hue and fastness with a small number of steps, low fixed cost and variable cost (raw material cost, etc.), and has a small drainage load. It is an object of the present invention to provide a printing method for polyester fiber materials having excellent economic efficiency and ecological properties.

In order to achieve the above object, the present inventor has conducted extensive research on a printing method for polyester fiber materials by a gravure printing method using an aqueous dispersion ink, and as a result, a specific method among papers on the market has been obtained. According to the printing method, which uses the base paper and applies the gravure printing method using the aqueous gravure ink of the disperse dye developed by us to prepare the transfer paper, and then transfers and prints the polyester fiber material using this transfer paper. With a small number of processes, low fixed costs and variable costs (raw material costs, etc.), it is possible to stably produce polyester fiber materials with excellent quality such as hue and fastness, and this printing method has a small drainage load. We have completed the present invention, which is a transfer printing method for polyester fiber materials having excellent heading, economic efficiency and ecology.

The first invention of the present invention is
For base paper with surface Beck smoothness of 50 seconds or more and 15,000 seconds or less
It contains finely divided disperse dye having an average particle size of 0.1 μm or more and 10 μm or less, a water-miscible organic solvent, a viscosity modifier, and water, and has a viscosity (25 ° C.) of 30 mPas or more and 800 mPas. The step of printing with the following water-based gravure ink to prepare a transfer paper, and the transfer paper is brought into close contact with the polyester fiber material and pressed and heated to convert the water-based gravure ink into the polyester fiber material. Consists of the process of transfer printing
The transfer printing method for a polyester fiber material is characterized in that the pressurization / heating is performed at a transfer temperature of 140 ° C. or higher and 250 ° C. or lower, and a transfer pressure of 0.01 MPa or higher and 5 MPa or lower (claim 1). ).

The second invention of the present invention is a preferred embodiment of the first invention.
A transfer printing method for a polyester fiber material, wherein the water-miscible organic solvent contained in the water-based gravure ink is a monoalcohol having 1 to 5 carbon atoms (claim 2).

The third invention of the present invention is a preferred embodiment of the first or second invention.
A transfer printing method for a polyester fiber material, characterized in that the viscosity (25 ° C.) of the aqueous gravure ink is 50 mPas or more and 500 mPas or less (claim 3).

The fourth invention of the present invention is a preferred embodiment of any one of the first to third inventions.
The viscosity modifier contained in the water-based gravure ink is water-soluble polyvinyl alcohol and its derivative, water-soluble polyacrylic acid ester and its derivative, water-soluble polyurethane and its derivative, water-soluble polyethylene oxide and its derivative, water-soluble polyamide and Its derivatives, water-soluble copolymers of styrene and acrylic acid and their derivatives, water-soluble polyesters and their derivatives, polyethylene glycol, glycerin, polyvinylpyrrolidone, natural gum paste, fibrous derivatives, polysaccharides, seaweeds, and animal products. A transfer printing method for a polyester fiber material, which is one or more selected from the group consisting of sizing agents (claim 4).

The fifth invention of the present invention is a preferred embodiment of any one of the first to fourth inventions.
The aqueous gravure ink is a dye dissolving agent, a dispersant, a surfactant, a moisturizing agent, a pH adjusting agent, a deep dyeing agent, a preservative, a fungicide, a degassing agent, a defoaming agent, an antioxidant, and a metal. A transfer printing method for a polyester fiber material, which further contains one or more auxiliary agents selected from the group consisting of ion sequestering agents (claim 5).

The sixth invention of the present invention is a preferred embodiment of any one of the first to fifth inventions.
A transfer printing method for a polyester-based fiber material, wherein the base paper is a single-gloss paper, a calendered coated paper, a glassine paper, a cellophane paper, or a cast-coated paper (claim 6).

The seventh invention of the present invention is a preferred embodiment of any one of the first to sixth inventions.
A transfer printing method for a polyester fiber material, characterized in that the basis weight of the base paper is 20 to 120 g / m ² (claim 7).

The eighth invention of the present invention is a preferred embodiment of any one of the first to seventh inventions.
The polyester fiber material comprises a filament, a spun yarn woven fabric, a knitted fabric, a non-woven fabric, a sheet or a film of a polyester-based polymer, or the woven fabric, a knitted fabric or a non-woven fabric, and synthetic fibers other than natural fibers and polyester-based polymers. A transfer printing method for a polyester-based fiber material, which is a blended fiber, a mixed fiber, a mixed woven product, or a composite material with a fiber selected from the group (claim 8).

The present invention also provides a method for producing a transfer paper (claim 9), which comprises using a transfer printing method for a polyester fiber material, which is any one of the first to eighth inventions.

The present invention is further characterized by being produced by a transfer printing method for a polyester fiber material according to any one of the first to eighth inventions (claim 10). I will provide a.

The transfer printing method of the polyester fiber material of the present invention is a transfer printing method capable of printing a polyester fiber material using a disperse dye to finish a product having a fine, robust and good texture, and is an inexpensive base paper. In addition to using transfer paper obtained by printing ink on the paper, it is characterized in that many steps required in the conventional transfer printing method are performed in one step. In addition, the drainage load is also small. That is, it is a novel transfer printing method that has excellent cost competitiveness and economic efficiency, is also excellent in ecology, and can provide products of excellent quality.

For example, in the case of a known dry transfer printing method, three steps of a transfer step, a fixing (steaming) step, and a washing step are indispensable, but according to the present invention, the entire transfer printing step is performed in one step of the thermal transfer step. It can be completed (therefore, the method of the present invention is called a one-shot method (one-step method)). Therefore, the process is simple and economical, and since the cleaning process is unnecessary, no drainage is generated and there is no drainage load, so that the ecology is excellent.

In the present invention, as the base paper for producing the transfer paper, an inexpensive base paper such as single-gloss paper, coated paper, glassin paper, cellophane paper, cast-coated paper to which no special adhesive is applied is used. Therefore, this is also an economical method.

According to the transfer printing method of the polyester fiber material of the present invention, a polyester fiber material having good dyeing power (color development property) can be obtained. When a non-sublimation type disperse dye is used, a printed product having good fastness and texture can be obtained even if the cleaning step is omitted.

Further, according to the present invention, an existing roller type (also referred to as a rotary type or continuous type) sublimation transfer machine or a flat plate type heat transfer device, which is widely used in the dyeing industry, is utilized to prepare a polyester synthetic fiber material. Robust and highly transferable printing is possible. And while taking advantage of this advantage and the advantage of being able to use an inexpensive commercially available base paper, the quality such as uniform dyeing property, texture, fineness, color development and fastness is good, and economic efficiency and ecology (drainage). An excellent printing method (such as zero load) can be constructed.

Currently, oil-based ink is used for gravure printing of sublimation transfer paper in the sublimation transfer method, but there are problems in terms of human safety and health, and there are also problems of environmental pollution. Since the water-based gravure ink is used in the present invention, this problem is solved. As is clear from the above description, the present invention provides an ecological and economic transfer printing method that is kind to the earth.

[Base paper]
In the present invention, as the base paper for gravure printing, a base paper having a surface Beck smoothness of 50 seconds or more and 15,000 seconds or less, preferably 100 seconds or more and 5000 seconds or less is used. The Beck smoothness of the surface is a measured value of the measurement performed in accordance with JIS P8119, and is a value indicating the smoothness of the surface of the paper. If a base paper having a Beck smoothness of less than 50 seconds is used, printability and color development (dyeing power at the time of transfer) become insufficient. On the other hand, if a base paper having a Beck smoothness of more than 15,000 seconds is used, the printability (ink flow and bleeding) is lowered.

Examples of the paper having a surface Beck smoothness of 50 seconds or more and 15000 seconds or less include known single-gloss paper, coated paper, glassin paper, cellophane paper, and cast-coated paper, and the smoothness selected from these can be mentioned. Excellent paper can be used as the base paper. Although some cellophane papers and the like have a surface Beck smoothness of more than 15,000 seconds, the one that can be used as a base paper in the present invention has a surface Beck smoothness of 15,000 seconds or less.

As described in JP-A No. 10-25690 and JP-A-2011-12357, for example, paper-making chemicals (sizing agent, size fixing agent, paper strength enhancer, etc.) are prepared by using pulp fiber as a main raw material. ) Is added to the paper, and the wet paper is dried by adhering to the mirror-finished Yankee dryer mirror surface. A large number of methods for producing single-gloss paper are disclosed in JP-A-7-78318, JP-A-2009-79326, JP-A-2009-138294, Patent No. 4885100, and the like. It is also possible to use the improved single-gloss paper.

Further, as the single gloss paper, it is also possible to use a single gloss paper in which a coating layer is provided on a base paper such as high-quality paper or kraft paper as described in Japanese Patent Publication No. 6-94229. is there. The structure of the Yankee dryer used for single-gloss paper is described in Paper Pa Gikyo Magazine Vol. 54, No. 11, p. 27.

The coated paper is described in JP-A-5-125695, JP-A-2004-21219, Patent No. 2612441, JP-A-2003-113594, etc., and includes calcium carbonate, kaolin clay, talc, and rubber latex. , Processed starches, natural adhesives such as casein, and synthetic adhesives such as polyvinyl alcohol and styrene butadiene latex are applied with an on-machine or off-machine coater equipped with a coating device, and then a super calendar or soft calendar. It is a paper whose surface smoothness has been improved by a finishing device such as.

Coated paper is an inexpensive paper that is mass-produced as paper for posters, calendars, advertising villas, insert advertisements, etc., and has good printability, but it is coated for the purpose of an ink receiving layer for transfer printing. It's not paper. When printing on coated paper with an inkjet printer, bleeding is severe because the ink receiving layer for the ink of the inkjet printer is not formed. Since the ink receiving layer is transferred to the fiber material at the time of transfer printing, a cleaning step of the fiber material is required after the transfer, but the coat layer of the coated paper is not transferred to the fiber material at the time of transfer printing. That is, the coated paper used in the present invention is a paper having a coating layer that does not transfer to the fiber material at the time of transfer printing.

The glassine paper is described in, for example, Japanese Patent Application Laid-Open No. 7-60905, Japanese Patent Application Laid-Open No. 6-192992, Japanese Patent Application Laid-Open No. 2569356, Japanese Patent Application Laid-Open No. 2016-503840, etc., and contains coniferous chemical pulp as a main compounding component. It is a translucent base paper that is made by beating pulp strongly to make paper with acidity or neutrality, and then densifying it with finishing equipment such as a super calendar. Various auxiliary agents (size agent, paper strength enhancer, yield improver, pigment, etc.) may be added to this paper in the papermaking process, as described in JP-A-9-176999. , Glassine paper coated with a water-soluble polymer can also be used.

As described in Japanese Patent Application Laid-Open No. 10-265587, cellophane paper is processed with pulp to form viscose, formed through a slit in a coagulation bath, refined, and finally adhere-dried with a cylinder in a dryer. It was made to do.

The cast coated paper is described in JP-A-6-74558, JP2010-180489, JP2012-197542, JP2011-733668, Patent No. 2817643, etc., and is a pigment. (Kaolin clay, calcium carbonate, etc.), adhesives (soybean protein, latex, polyacrylic acid, PVA, etc.), auxiliaries (formic acid, formic acid derivatives, defoamers, surfactants, water resistant agents, antioxidants, water retention It can be obtained by applying a cast coating liquid composed of an agent, a mold release agent, etc.) to the surface of the base paper, and then pressure-contacting and drying the cast drum dryer having a mirror surface gloss. The cast-coated paper used in the present invention is also a paper having a coating layer that does not transfer to the fiber material during transfer printing.

Examples of the pulp forming the base paper include unbleached or bleached coniferous pulp, hardwood pulp, kraft pulp, grind pulp, and recycled pulp made from recycled paper. The base paper obtained from these pulps can contain sizing agents, paper strength enhancers, fillers, pigments, etc., to improve the dimensional stability of the paper, and to suppress water absorption and wrinkles. , The base paper containing fine silica, clay, water-soluble synthetic resin, processed starch, etc. on or in the paper may be used.

From the viewpoint of workability, the basis weight of the base paper is preferably 20 g / m ² or more and 120 g / m ² or less, and more preferably 25 g / m ² or more and 80 g / m ² or less. When the basis weight is less than 20 g / m ² , problems such as weakening of the strength of the paper and easy occurrence of wrinkles are likely to occur, and the workability of various work processes is lowered. On the other hand, if it exceeds 120 g / m ² , the color development property deteriorates. Further, there are problems such as an increase in the cost of the base paper, a decrease in the flexibility and heat transfer property of the paper, and a decrease in work efficiency. The thickness of the base paper is preferably about 0.01 to 0.5 mm from the viewpoint of workability and the like.

Single glossy paper, coated paper, glassine paper, cellophane paper, and cast coated paper are commercially available. Specific examples of single-gloss paper include silver bamboo (basis weight 41.7, 50, 58.3, 66.6, 83.3 g / m ² ), which is unbleached single-gloss kraft paper manufactured by Nippon Paper Co., Ltd. Capital wrap (basis weight 50, 60, 70, 80, 100, 120 g / m ² ), white silver (basis weight 30 to 65 g / m ² ), A Ginrei N (basis weight 30, 35 g / m), which is a glossy bleached kraft paper. ² ) Strained, Ryuou Coat manufactured by Daio Paper Co., Ltd., Utrilogros Matte, Yankee Paper (basis weight 20-120 g / m ² ), single gloss kraft paper manufactured by Maruzumi Paper Co., Ltd., Star White (basis weight 30, 35, 40, 45 g / m ² ), Star Pack A (basis weight 50 to 120 g / m ² ), Star Pack A-F (basis weight 30 to 150 g / m ² ) and the like can be mentioned.

In addition, Daiko Paper Co., Ltd.'s single-gloss kraft metal interleaving paper (basis weight 40 g / m ² ), masking base paper (basis weight 40 g / m ² ), acid-free paper for food (basis weight 40 g / m ² ), print for building materials A base paper (basis weight 23 to 60 g / m ² ) and the like can also be mentioned as an example. As the single-gloss paper that can be used in the present invention, double-sided glossy paper that is made by a Yankee machine and further finished with a super calender can also be used as the single-gloss paper in the present invention.

Specific examples of coated paper include Aurora Coat, Aurora L, Silver Diamond DRY, MI Gloss 60 (basis weight 62, 67 g / m ² ), MI Gloss WX (basis weight 60, 64, 72, 78) manufactured by Nippon Paper Industries Limited. , 98g ^{/ m} 2), manufactured by Mitsubishi Paper Mills of N Pearl coat L (basis weight 64,69.9,72.3g ^{/ m} 2), Vista gloss NA (64,72.3g ^{/ m} 2), umbrella Deer gloss Examples include A, Dignity, Pearl Coat N, etc., OK Top Coat manufactured by Oji Paper Mills, and Mucoat Neo manufactured by Hokuetsu Paper Mills.

Specific examples of glassine paper include glassine paper manufactured by Nippon Paper Industries (basis weight 25.8, 30.5, 35, 40 g / m ² ), moisture-resistant glassine paper (basis weight 30.5, 40 g / m ² ), and milky white. Glassine paper (30.5 g / m ² ) and the like can be mentioned as an example.

Specific examples of the cellophane paper include ordinary cellophane (PT) and white cellophane (PCW) manufactured by Rengo Co., Ltd. As a cellulosic film similar to cellophane, a cellulose acetate film can also be used as cellophane paper.

Cast coated paper is also called mirror coated paper, and specific examples include the Esprit series manufactured by Nippon Paper Industries, single-sided chrome color of Oji special paper, and double-sided chrome color.

In the present invention, it is not necessary to form an ink receiving layer on the base paper. That is, although the above-mentioned various base papers are commercially available as inexpensive papers, transfer papers can be produced by using these inexpensive base papers without forming an ink receiving layer. The various physical characteristics of the base paper, such as air permeability, density, tensile strength, surface strength, and wet strength, are not particularly limited, and various physical properties are used as long as they do not have a significant adverse effect on workability. it can.

[dye]
A transfer paper can be obtained by applying (printing) a disperse dye to the base paper in the form of ink by a gravure printing method. As the disperse dye used here, either a sublimation type disperse dye (E type) or a non-sublimation type disperse dye (S type or SE type) can be used. However, non-sublimation type disperse dyes that are difficult to sublimate at high temperatures and have excellent fastness are preferable.

As a non-sublimation type disperse dye,
C. I. Disperse Yellow 49, 56, 58, 63, 67, 76, 79, 82, 86, 114, 121, 123, 126, 149, 163, 165, 180, 184, 185, 192, 198, 222, 226, 228 , 231
C. I. Dispers Orange 10, 13, 17, 21, 29, 30, 32, 50, 51, 55, 61, 62, 73, 96, 97, 148,
C. I. Dispers Red 5, 12, 13, 17, 43, 54, 56, 58, 64, 72, 73, 74, 76, 78, 82, 86, 88, 90, 92, 97, 107, 109, 113, 121 , 125, 126, 127, 128, 129, 134, 135, 136, 137, 140, 143, 145, 151, 152, 153, 154, 160, 167, 177, 179, 181, 183, 184, 188, 189. , 191, 202, 205, 210, 221, 225, 257, 258, 283, 285, 288, 302, 233, 356, 360,
C. I. Dispers Violet 26, 33, 35, 40, 43, 46, 48, 52, 58, 63, 69, 77, 92,
C. I. Disperse Blue 7, 27, 40, 54, 60, 62, 73, 75, 77, 79, 82, 83, 85, 87, 90, 94, 96, 99, 102, 103, 104, 113, 122, 125 , 128, 130, 139, 142, 143, 144, 146, 148, 158, 165, 167, 173, 174, 176, 181, 183, 197, 198, 200, 201, 207, 211, 214, 257, 259. 264, 266, 270, 301, 354,
C. I. Dispers Brown 1, 4, 9, 13, 19, 24, 25 and the like can be mentioned. Black can be produced by blending the above three primary colors of the non-sublimation type disperse dye + α.

Further, as a specific example of the sublimation type disperse dye, the dye described in claim 9 of Japanese Patent Application Laid-Open No. 2011-21133 can be mentioned. Many of these sublimation type disperse dyes have low fastness as a whole, including sublimation fastness and light fastness.

The disperse dye is inked so that it can be used as a gravure ink. After being converted into ink, ink is printed (printed) on the base paper (base paper having no special ink receiving layer) by gravure printing to produce a transfer paper. The dye content (pigment base) in the ink is preferably 1 to 20% by mass, and is adjusted by the color density. When the ink used is oil-based ink, there are many problems such as workplace safety and health, environmental problems, handling of dangerous substances, economy, etc. However, since water-based ink is used in the present invention, these problems have been solved.

As the disperse dye in the gravure printing ink (gravure ink), those finely divided to an average particle size of 0.1 μm or more and 10 μm or less are used. If the average particle size is too small or too large, printability and color development tend to be poor. The disperse dye is preferably atomized in water with the dispersant.

[Aqueous gravure ink / transfer paper]
In gravure printing for producing transfer paper, a dye atomized together with a dispersant is mixed and dispersed in a viscous aqueous solution containing a viscosity modifier to adjust the viscosity to about 30 to 800 mPas, preferably 50 mPas or more and 500 mPas or less. Aqueous gravure ink adjusted to can be used. Dispersants that can be used include formalin naphthalin sulphonate, methyl or formalin butyl naphthaline sulphonate, lignin sulphonic acid, olphin PD-003, olphin PD-001, olphin PD-002W, olphin PD-004, olphin PD. -005, Orfin PD-201, Orfin PD-301 and the like can be mentioned.

The viscosity modifier is added to adjust the viscosity of the ink. Examples of the viscosity modifier include water-soluble polyvinyl alcohol and its derivatives, water-soluble polysaccharide ester and its derivatives, water-soluble polyurethane and its derivatives, water-soluble polyethylene oxide and its derivatives, water-soluble polyamide and its derivatives, styrene and acrylic. Water-soluble copolymers of acids and their derivatives, water-soluble polyesters and their derivatives, polyethylene glycol, glycerin, polyvinylpyrrolidone, natural gum paste, fibrous derivatives, polysaccharides, seaweeds, animal pastes, etc. And one or more selected from these can be used.

More specific examples of water-based inks for gravure printing include Metrose 65SH / 400 (manufactured by Shin-Etsu Chemical Co., Ltd.), Metrose 65SH / 4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Poval AP-17 (manufactured by Japan Vam & Poval Co., Ltd.). Using partially hydrolyzed PVA as a viscosity modifier, a disperse dye atomized to an average particle size of 0.1 to 10 μm is contained in an amount of 1 to 20% by mass in terms of dye base, and the viscosity of the printing ink is 30 to 800 mPas. More preferably, an ink adjusted to 50 to 500 mPas can be used.

The water-based gravure ink contains a water-miscible organic solvent. By containing a water-miscible organic solvent, good printability and drying property can be obtained. As the water-miscible organic solvent, monoalcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and pentanol are preferable, and isopropanol is particularly preferable. The content of the monoalcohols having 1 to 5 carbon atoms is preferably 10% by mass or more and 60% by mass or less of the total content of the monoalcohols having 1 to 5 carbon atoms and the water. If the content is less than 10% by mass, printability and dryness are deteriorated. On the other hand, if it exceeds 60% by mass, the dye tends to aggregate, making it difficult to uniformly disperse the dye, and the ink becomes a dangerous substance under the Fire Service Act.

The water-based gravure ink preferably contains an auxiliary agent. Auxiliary agents include dye solubilizers, dispersants, surfactants, moisturizers, pH regulators, dark dyes, preservatives, fungicides, deaerators, defoamers, redox inhibitors, and metal ions. A sequestering agent can be mentioned, and one or more selected from the group consisting of these is blended in the ink.

[Transfer printing process]
The transfer printing of the present invention is carried out by superimposing the transfer paper obtained as described above and the polyester-based fiber material (fabric), and transferring and dyeing the dye on the fiber material by pressurizing and heating. Pressurization / heating is performed in a temperature range of 140 ° C. or higher and 250 ° C. or lower, and a pressure (transfer pressure) of 0.01 MPa or higher and 5 MPa or lower. If the temperature or pressure exceeds the upper limit, the texture of the product tends to be inferior, while if the temperature or pressure is less than the lower limit, the color development tends to be insufficient. In the case of the non-sublimation type disperse dye, the pressure is preferably in the range of 0.02 MPa or more and 2 MPa or less, more preferably 0.02 MPa or more and 0.3 MPa or less in terms of texture and color development.

The time for pressurization / heating (treatment time, transfer time) is usually in the range of 1 second to 10 minutes, but the higher the temperature and pressure, the shorter the treatment time and the better the color development. In order to improve the property, the higher the temperature and the higher the pressure, the more preferable. For example, in the case of a sublimation type disperse dye, excellent color development can be obtained at a transfer temperature of 190 to 200 ° C., a transfer pressure of 0.01 to 0.05 MPa, and a treatment time of 30 to 90 seconds. In the case of the non-sublimation type disperse dye, excellent color development property with good fastness can be obtained at a transfer temperature of 220 ° C., a transfer pressure of 0.03 MPa, and a treatment time of 40 to 120 seconds.

[Polyester fiber material]
The polyester fiber material to be transferred and printed by the transfer printing method of the present invention includes a woven fabric, a knitted fabric, a non-woven fabric, a sheet, a film, etc. mainly made of a polyester-based polymer material, or the above-mentioned woven fabric, knitted fabric, non-woven fabric, etc. Examples thereof include fiber materials such as blended fibers with synthetic fibers other than natural fibers and polyester-based polymer materials, mixed fibers, mixed woven fabrics, and composite materials. Examples of the polyester-based polymer material include polyester-based materials called polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, depolymerized polyester, cationic dyeable polyester, room temperature dyeable polyester, and alkali weight loss polyester. .. Examples of the natural fiber include cellulosic fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk and wool. The synthetic fiber material means all known synthetic fiber materials other than polyester-based polymer materials such as nylon, vinylon, polyacrylic, and polyurethane, and may be a composite fiber.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples. In the example, parts mean parts by mass and% means% by mass.

Example 1
Commercially available Utrilo coated paper (neutral paper, basis weight 46 g / m ² , Beck smoothness 1616 seconds, manufactured by Hokuetsu Kishu Co., Ltd.) was used as the base paper. Next, as a viscosity modifier, Metrose 65SH / 400 (manufactured by Shin-Etsu Chemical Co., Ltd.), Metrose 65SH / 4000 (manufactured by Shin-Etsu Chemical Co., Ltd.), and Poval AP-17 (manufactured by Japan Vam & Poval Co., Ltd.) were used and miscible with water. Isopropanol (30% with respect to the total amount of isopropanol and water) was used as the organic solvent to prepare a viscous ink liquid having a viscosity of 200 mPas. In this ink liquid, C.I. I. 20% of Disperse Red86 / 200% product (average particle size 1.2 μm) was blended (relative to the ink solution), and the viscosity of the ink was adjusted to 125 mPas to prepare Magenta ink for water-based gravure.

The magenta ink for gravure thus obtained was applied onto the above-mentioned single glossy paper at a speed of 10 to 20 m / min using an electric gravure printing tester GP-10 (manufactured by Kurabo Industries Ltd.). A transfer paper was obtained by printing (solid printing) at a temperature of 25 ° C. The transfer paper and the polyester taffeta dough are brought into close contact with each other and heated and pressurized (220 ° C., roll pressure 0.2 Mpa, roll contact time 90 seconds, roller type transfer machine) to transfer the dye to the dough, and then the paper. Was removed to obtain a polyester printed cloth. The polyester textile printed cloth obtained in this way is densely and delicately dyed, the texture of the fibers is good, and both the sunlight fastness (variant) and the sublimation fastness (variant, dirty) are grade 5. That was all.

Example 2
As an ink for water-based gravure, C.I. I. Disperse Red92 200% product 20% is blended and the viscosity is adjusted to 110 mPas using water, cellulosic viscosity modifier, polyvinyl alcohol and isopropanol (30% of the total amount of isopropanol and water) to make water-based gravure ink. Was produced. Using this water-based gravure ink, print on commercially available Utrilo coated paper (acid-free paper, basis weight 55 g / m ² , Beck smoothness 3559 seconds, manufactured by Hokuetsu Kishu Co., Ltd.) under the same conditions as in Example 1. I got a transfer paper.

The transfer paper thus obtained is brought into close contact with the polyester taffeta dough, and heated and pressurized (220 ° C., cylinder pressure 0.8 Mpa, 40 seconds) using a flat plate press manufactured by Hashima Co., Ltd. to apply the dye to the dough. After the migration, the paper was removed to obtain a polyester textile. The polyester textile printed cloth thus obtained is densely dyed, the texture of the fibers is good, and the sublimation fastness by JISL0854 is (variant) 4-5 grade and (dirty) 4-5 grade. there were. Moreover, the light fastness according to JISL0842 was 5th grade or higher.

Example 3
Treatment in the same manner as in Example 2 except that commercially available glassine paper (basis weight 35 g / m ² , Beck smoothness 256 seconds, manufactured by Nippon Paper Industries Co., Ltd.) is used instead of the commercially available Utrilo coated paper in Example 2. A robust, dark polyester textile was obtained.

Example 4
Except for using commercially available single-gloss bleached kraft paper (basis weight 60 g / m ² , Beck smoothness 126 seconds, manufactured by Hokuetsu Kishu Co., Ltd.) instead of the commercially available Utrilo coated paper in Example 2, the same as in Example 2. The same treatment was performed to obtain a tough, dark polyester fabric.

Example 5
Similar to Example 2 except that a commercially available capital wrap paper (basis weight 50 g / m ² , Beck smoothness 2650 seconds, manufactured by Nippon Paper Industries Co., Ltd.) is used instead of the commercially available Utrilo coated paper in Example 2. The treatment gave a tough, dark polyester knit.

Example 6
Example 2 except that a commercially available pure white roll paper (gold killer whale, basis weight 30 g / m ² , Beck smoothness 190 seconds, manufactured by Daio Paper Corporation) is used instead of the commercially available Utrilo coated paper in Example 2. The same treatment was performed to obtain a tough, dark-colored polyester printed cloth.

Example 7
Examples except that commercially available N Kinto single-sided L (acid paper, basis weight 59 g / m ² , Beck smoothness 378 seconds, manufactured by Daio Paper Corporation) is used instead of the commercially available Utrilo coated paper in Example 2. The same treatment as in No. 2 was performed to obtain a tough, dark-colored polyester printed cloth.

Example 8
Treated in the same manner as in Example 2 except that commercially available cellophane paper (basis weight 30 g / m ² , Beck smoothness 7560 seconds, manufactured by Rengo Co., Ltd.) was used instead of the commercially available Utrilo coated paper in Example 2. As a result, although some ink flow was observed, a robust and dark polyester printed cloth was obtained.

Example 9
Examples except that a commercially available mirror-coated paper (basis weight 65 g / m ² , Beck smoothness 3478 seconds, manufactured by Nippon Paper Industries, cast-coated paper) is used instead of the commercially available Utrilo-coated paper in Example 2. The same treatment as in No. 2 was performed to obtain a tough, dark-colored polyester printed cloth.

Comparative Example 1
Treatment was carried out in the same manner as in Example 2 except that high-quality paper (manufactured by Nippon Paper Industries Co., Ltd.) having a basis weight of 65 g / m ² and a Beck smoothness of 45 seconds was used instead of the commercially available Utrilo-coated paper in Example 2. , It was judged that the printability and color development were poor and not practical.

Comparative Example 2
As a result of treating in the same manner as in Example 6 using the aqueous inkjet disperse dye ink described in Patent Document 5 or 7 instead of the water-based gravure ink in Example 6, bleeding is large and color development is poor. So, I decided that it was not practical.

Claims (9)

For base paper with surface Beck smoothness of 50 seconds or more and 15,000 seconds or less
It contains finely divided non-sublimation type disperse dye having an average particle size of 0.1 μm or more and 10 μm or less, a water-miscible organic solvent, a viscosity modifier, and water, and the viscosity (25 ° C.) is 50 mPas. As described above, the step of printing with a water-based gravure ink of 500 mPas or less to prepare a transfer paper, and the transfer paper being brought into close contact with a polyester fiber material and pressurized / heated to obtain the water-based gravure ink into the polyester-based material. It consists of the process of transferring and printing on textile materials.
A transfer printing method for a polyester fiber material, wherein the pressurization / heating is performed at a transfer temperature of 140 ° C. or higher and 250 ° C. or lower, and a transfer pressure of 0.01 MPa or higher and 5 MPa or lower. The transfer printing method for a polyester fiber material according to claim 1, wherein the water-miscible organic solvent contained in the water-based gravure ink is a monoalcohol having 1 to 5 carbon atoms. The viscosity modifier contained in the water-based gravure ink
Water-soluble polyvinyl alcohol and its derivatives, water-soluble polysaccharide ester and its derivatives, water-soluble polyurethane and its derivatives, water-soluble polyethylene oxide and its derivatives, water-soluble polyamide and its derivatives, water-soluble copolymer of styrene and acrylic acid One or 2 selected from the group consisting of coalescing and derivatives thereof, water-soluble polyesters and derivatives thereof, polyethylene glycol, glycerin, polyvinylpyrrolidone, natural gum paste, fibrous derivatives, polysaccharides, seaweeds, and animal pastes. The transfer printing method for a polyester-based fiber material according to claim 1 or 2 , characterized in that it is more than one species. The aqueous gravure ink is a dye dissolving agent, a dispersant, a surfactant, a moisturizing agent, a PH adjusting agent, a deep dyeing agent, a preservative, a fungicide, a degassing agent, a defoaming agent, an antioxidant, and a metal. The transfer printing of the polyester fiber material according to any one of claims 1 to 3, further containing one or more auxiliary agents selected from the group consisting of ion sequestering agents. Law. The polyester-based fiber material according to any one of claims 1 to 4, wherein the base paper is a single glossy paper, a calendered coated paper, a glassin paper, a cellophane paper, or a cast coated paper. Transfer printing method. The transfer printing method for a polyester fiber material according to any one of claims 1 to 5, wherein the base paper has a basis weight of 20 to 120 g / m ² . The polyester-based fiber material comprises a polyester-based polymer, filament, spun yarn woven fabric, knitted fabric, non-woven fabric, sheet or film, or the woven fabric, knitted fabric or non-woven fabric, and synthetic fibers other than natural fibers and polyester-based polymer. The transfer printing method for a polyester fiber material according to any one of claims 1 to 6, wherein the polyester fiber material is a blended fiber, a blended fiber, a mixed woven fabric, or a composite material with a fiber selected from the group. A method for producing a transfer paper used in the transfer printing method for a polyester fiber material according to any one of claims 1 to 7 . A method for producing a transfer-printed polyester-based fiber material, which comprises printing the polyester-based fiber material by the transfer-printing method for the polyester-based fiber material according to any one of claims 1 to 8 .