JP2022021342A - Manufacturing method of decorative product, and decorative product - Google Patents

Abstract

To provide a manufacturing method of a decorative product capable of printing on-demand a small quantity of various designs, having high color development, and hardly spoiling feeling of a fabric.SOLUTION: A manufacturing method of a decorative product includes: a step of preparing a transfer film having a printed layer directly formed on a base material by using an aqueous inkjet ink which is an aqueous inkjet ink containing water, a pigment, water-soluble organic solvent components, a silicone surface active agent and resin fine particles, and containing 9 mass% or more and 27 mass% or less of at least one kind of substituted butanol selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol, and in which the resin fine particles are fine particles of urethane resin having a glass transformation temperature of 0°C or less, and a content of the resin fine particles in the ink is 2.5 mass% or more; and a step of sticking the printed layer of the transfer film and a transferred surface of a fabric so as to transfer the printed layer.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a decorative item in which a cloth is printed. The present invention also relates to decorative products in which a fabric is printed.

Conventionally, in order to decorate a cloth, characters, images and the like have been printed on the surface of the cloth. Specifically, since ancient times, the screen printing method has been used to print a large number of patterns of the same design, but in recent years, there has been an increase in demand for a decoration method that can print various designs in small quantities on demand. ing.

As one of the methods suitable for small-quantity printing of various designs on demand, there is a method of forming an image or the like on a cloth with inkjet ink using a DTG (direct to garment) printer. However, this method has a drawback that it is difficult to obtain high color development, and it is possible to obtain high color development when a large amount of ink is used, but in this case, the thickness of the print layer becomes large. There is a drawback that the texture of the fabric is impaired.

Another method suitable for small-quantity printing of various designs on demand includes a method of transferring an image or the like onto a cloth using a transfer film (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2019-38112 Japanese Unexamined Patent Publication No. 10-315695

However, the technique described in Patent Document 1 has a drawback that the texture of the cloth is impaired because the ink receiving layer is transferred to the cloth together with the ink layer. The technique described in Patent Document 2 also has a drawback that the texture of the fabric is impaired because the thermal transfer layer is transferred to the fabric together with the ink layer.

It is an object of the present invention to provide a method for manufacturing a decorative item, which can print a wide variety of designs on demand in a small amount, has high color development, and does not easily impair the texture of the fabric.

The method for producing a decorative product according to the present invention is an aqueous solution containing at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin fine particles (E). An inkjet ink, the ink is at least one selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). The substituted butanol is contained in an amount of 9% by mass or more and 27% by mass or less, and the resin fine particles (E) are fine particles of a urethane resin having a glass transition temperature of 0 ° C. or less, and the resin fine particles (E) are contained in the ink. The step of preparing a transfer film provided with a printing layer directly formed on a film substrate using an aqueous inkjet ink having an amount of 2.5% by mass or more, the printing layer of the transfer film, and the cloth. It includes a step of adhering the surface to be transferred and transferring the printed layer.

From another aspect, the decorative article according to the present invention includes a cloth and a printing layer in contact with the cloth. The printing layer is a water-based inkjet ink containing at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin fine particles (E). The ink contains 9 parts by mass of at least one substituted butanol selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). The resin fine particles (E) containing% or more and 27% by mass or less are fine particles of urethane resin having a glass transition temperature of 0 ° C. or less, and the content of the resin fine particles (E) in the ink is 2.5. It is formed by using a water-based inkjet ink having a mass% or more, and the print layer is transferred onto the cloth.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for manufacturing a decorative product, which can print various designs in a small amount on demand, has high color development, and does not easily impair the texture of the fabric.

The method for producing a decorative product according to the present invention is an aqueous solution containing at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin fine particles (E). An inkjet ink, the ink is at least one selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). The substituted butanol is contained in an amount of 9% by mass or more and 27% by mass or less, and the resin fine particles (E) are fine particles of a urethane resin having a glass transition temperature of 0 ° C. or less, and the resin fine particles (E) are contained in the ink. A step of preparing a transfer film having a printing layer directly formed on a film substrate using an aqueous inkjet ink having an amount of 2.5% by mass or more (transfer film preparation step) and a step of preparing the transfer film. It includes a step (transfer step) of transferring the printed layer by laminating the printed layer and the surface to be transferred of the fabric.

<Transfer film preparation process>
Typically, the transfer film is prepared by printing on the film substrate by an inkjet recording method using an aqueous inkjet ink containing at least the components (A) to (E) described below. Can be done. It may be prepared by purchasing a transfer film produced by printing on a film substrate by an inkjet recording method using the water-based inkjet ink.

[Water (A)]
The water-based inkjet ink contains water (A). By containing water (A), the water-based inkjet ink has an advantage that the environmental load is small. The water (A) used is not particularly limited, but ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water is preferable, and ion-exchanged water is preferable from the viewpoint of preventing contamination with impurities. Is more preferable.

The content of water (A) in the water-based inkjet ink is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more. On the other hand, the content of water (A) is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.

[Pigment (B)]
As the pigment (B), either an inorganic pigment or an organic pigment can be used. The pigment (B) can be used alone or in combination of two or more at any ratio.

Examples of organic pigments include azo pigments (eg, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc.), dye chelate (eg, basic dye type chelate, acidic dye type chelate, etc.), nitro pigments, nitroso pigments, aniline black, etc. ..

Examples of inorganic pigments are titanium oxide, zinc flower, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, bengara, molybdenum. Red, Molybdate Orange, Chrome Vermillion, Yellow Lead, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chromium Oxide, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine, Navy Blue, Cobalt Blue, Cerulean Examples include blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet and the like.

More specifically, examples of the black pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black; copper, iron (CI pigment black), and the like. Examples thereof include metals such as 11); metal oxides such as titanium oxide; and organic pigments such as aniline black (CI pigment black 1).

Examples of the cyan pigment include C.I. I. Pigment Blue 1,2,3,15: 1,15: 3,15: 4,15: 6,16,21,22,60,64 and the like.

Examples of magenta pigments include C.I. I. Pigment Red 5,7,9,12,31,48,49,52,53,57,97,112,120,122,146,147,149,150,168,170,177,178,179,184 188,202,206,207,209,238,242,254,255,264,269,282; C.I. I. Pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 40, 50 and the like.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1,2,3,12,13,14,16,17,20,24,74,83,86,93,94,95,109,110,117,120,125,128,129,137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213 and the like can be mentioned.

Examples of pigments of other colors include C.I. I. Pigment Green 7, 10, 36; C.I. I. Pigment Brown 3, 5, 25, 26; C.I. I. Pigment oranges 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 62, 63, 64, 71 and the like.

Further, a pigment having a hydrophilic group such as a carboxyl group, a sulfonic acid group, a phosphonic acid group and a hydroxyl group (so-called "self-dispersing pigment") can be used on the surface. Examples of the carbon black self-dispersing pigment include CAB-O-JET200, 300, 352K, 400 (all manufactured by Cabot Corporation) and the like. Examples of the cyanide self-dispersing pigment include CAB-O-JET250C, 450C, 554B (all manufactured by Cabot Corporation) and the like. Examples of the magenta self-dispersing pigment include CAB-O-JET260M, 265M, 465M (all manufactured by Cabot Corporation) and the like. Examples of the yellow self-dispersing pigment include CAB-O-JET270, 470Y, 740Y (all manufactured by Cabot Corporation) and the like. A self-dispersing pigment is preferable as the coloring material (B) because it can be dispersed in water (A) without using a dispersant.

The content of the pigment (B) in the water-based inkjet ink is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, as the solid content (solid content concentration). On the other hand, the content of the pigment (B) is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less.

[Water-soluble organic solvent component (C)]
In the present specification, the "water-soluble organic solvent" constituting the water-soluble organic solvent component (C) means an organic solvent having a solubility in water at 20 ° C. of 500 g / L or more. The water-soluble organic solvent is preferably an organic solvent that is uniformly miscible with water at an arbitrary ratio at 20 ° C.

The water-based inkjet ink used here is a substitution of at least one selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). It contains butanol in an amount of 9% by mass or more and 27% by mass or less. This substituted butanol is a component that improves the initial drying rate of the water-based inkjet ink. If the content of the substituted butanol is less than 9% by mass, the initial drying rate becomes slow, image bleeding occurs, the image quality deteriorates, and as a result, the color development property deteriorates. The content of the substituted butanol in the water-based inkjet ink is preferably 10% by mass or more, more preferably 12% by mass or more. On the other hand, when the content of the substituted butanol exceeds 27% by mass, the initial drying rate becomes too fast, cracks occur in the print layer, the image quality deteriorates, and as a result, the color development property deteriorates. The content of the substituted butanol is preferably 25% by mass or less, more preferably 23% by mass or less, still more preferably 20% by mass or less.

The water-based inkjet ink may contain a water-soluble organic solvent other than the above-mentioned substituted butanol as the water-soluble organic solvent component (C). As the water-soluble organic solvent other than the substituted butanol, a known water-soluble organic solvent for the water-based inkjet ink can be used without particular limitation.

Since the water retention property of the water-based inkjet ink is improved, diols are suitable as a water-soluble organic solvent other than the above-mentioned substituted butanol. Examples of diols include ethylene glycol (boiling point: about 196 ° C.), diethylene glycol (boiling point: about 244 ° C.), triethylene glycol (boiling point: about 287 ° C.), propylene glycol (boiling point: about 188 ° C.), and dipropylene glycol. (Boiling point: about 230 ° C.), 1,3-Propanediol (boiling point: about 213 ° C.), 1,2-butanediol (boiling point: about 194 ° C.), 2,3-butanediol (boiling point: about 183 ° C.), 1,3-Butanediol (boiling point: about 208 ° C), 2,2-dimethyl-1,3-propanediol (boiling point: about 208 ° C), 2-methyl-1,3-propanediol (boiling point: about 213 ° C) ), 1,2-Pentanediol (boiling point: about 206 ° C), 2,4-pentanediol (boiling point: about 201 ° C), 2-methyl-2,4-pentanediol (boiling point: about 198 ° C), 1, 5-Pentandiol (boiling point: about 242 ° C), 1,2-hexanediol (boiling point: about 224 ° C), 1,6-hexanediol (boiling point: about 250 ° C), 2-ethyl-1,3-hexanediol (boiling point: about 250 ° C) Boiling point: about 243 ° C.) and the like. These can be used alone or in combination of two or more at any ratio. As the diols, diols having a linear or branched alkylene chain having 3 to 6 carbon atoms (particularly 4 to 5 carbon atoms) are preferable. Further, as the diols, a combination of 3-methyl-1,5-pentanediol and diols having 3 to 5 carbon atoms is preferable. The content of the diols in the water-based inkjet ink is preferably 1.5% by mass or more, more preferably 3.0% by mass or more. On the other hand, the content of the diols is preferably 20% by mass or less, more preferably 15% by mass or less.

Glycol monoethers are suitable as a water-soluble organic solvent other than the above-mentioned substituted butanol because the image quality is particularly high. Examples of glycol monoethers include triethylene glycol monobutyl ether (boiling point: about 278 ° C.), dipropylene glycol monomethyl ether (boiling point: about 190 ° C.), tripropylene glycol monomethyl ether (boiling point: about 242 ° C.), and propylene glycol. -N-butyl ether (boiling point: about 171 ° C.), propylene glycol-t-butyl ether (boiling point: about 153 ° C.), diethylene glycol monobutyl ether (boiling point: about 230 ° C.), diethylene glycol monoethyl ether (boiling point: about 202 ° C.), diethylene glycol Examples thereof include glycol monoethers such as monomethyl ether (boiling point: about 194 ° C.), ethylene glycol-n-propyl ether (boiling point: about 150 ° C.), and ethylene glycol-n-butyl ether (boiling point: about 171 ° C.). These can be used alone or in combination of two or more at any ratio. As the glycol monoethers, methyl ether, ethyl ether, propyl ether, or butyl ether of diethylene glycol, triethylene glycol, dipropylene glycol, or tripropylene glycol is preferable, and tripropylene glycol monomethyl ether is more preferable. The content of glycol monoethers in the water-based inkjet ink is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 3.0% by mass or more. On the other hand, the content of glycol monoethers is preferably 20% by mass or less, more preferably 15% by mass or less.

The water-based inkjet ink preferably contains both the above-mentioned diols and glycol monoethers as the water-soluble organic solvent component (C).

If the content of the water-soluble organic solvent component (C) in the water-based inkjet ink is too small, the drying property tends to decrease, and the wettability to the transfer film may decrease. Therefore, the content of the water-soluble organic solvent component (C) in the water-based inkjet ink is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and most preferably 25% by mass or more. .. On the other hand, if the content of the water-soluble organic solvent component (C) is too large, the ink viscosity tends to increase. Therefore, the content of the water-soluble organic solvent component (C) is preferably 55% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

In the present embodiment, a preferred embodiment of the water-based inkjet ink is 3-methoxy-1-butanol of 12% by mass or more and 20% by mass or less and 1% by mass or more and 8% by mass or less as the water-soluble organic solvent component (C). Tripropylene glycol monomethyl ether, 3-methyl-1,5-pentanediol, and diols having 3 to 5 carbon atoms are contained, and the content of the water-soluble organic solvent component (C) in the ink is , 25% by mass or more.

According to a preferred embodiment of this water-based inkjet ink, the occurrence of beading and cracking is suppressed, and it is possible to form a print layer of a transfer film having excellent blocking resistance.

In this preferred embodiment, the content of 3-methyl-1,5-pentanediol in the ink is preferably 2% by mass or more and 11% by mass or less, and more preferably 3% by mass or more and 10% by mass or less. More preferably, it is 4% by mass or 9% by mass or less. The content of the diols having 3 to 5 carbon atoms in the ink is preferably 2% by mass or more and 11% by mass or less, more preferably 3% by mass or more and 10% by mass or less, and further preferably 4% by mass% 9. It is less than mass%.

[Silicone-based surfactant (D)]
As the silicone-based surfactant (D), a known silicone-based surfactant can be used without particular limitation, and it is also available as a commercially available product. Examples of commercially available products include BYK-306, BYK-307, BYK-333, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (all manufactured by Big Chemie Japan), KF- 351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF- 6011, KF-6012, (above, manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG002, SAG005, SAG503A, SAG008 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned. As the silicone-based surfactant (D), a polyether-modified silicone-based surfactant is preferable.

The content of the silicone-based surfactant (D) in the inkjet ink may be appropriately determined so that the surface tension and the interfacial tension of the ink are optimized according to the type of the silicone-based surfactant used. The content of the silicone-based surfactant (D) in the water-based inkjet ink is preferably 0.05% by mass or more, more preferably 0.2% by mass or more. On the other hand, the content is preferably 5% by mass or less, more preferably 3.0% by mass or less, and further preferably 2.5% by mass or less.

[Resin fine particles (E)]
As the resin fine particles (E), urethane resin fine particles having a glass transition temperature (Tg) of 0 ° C. or lower are used. The water-based inkjet ink contains fine particles of urethane resin having a glass transition temperature of 0 ° C. or lower, so that the printed layer formed has excellent bending resistance and adhesiveness to fabric, and has excellent transfer quality. The print layer can be transferred to the fabric. In addition, only the print layer can be directly transferred to the fabric.

The glass transition temperature of the urethane resin is preferably −5 ° C. or lower, more preferably −10 ° C. or lower, still more preferably −15 ° C. or lower. There is no particular limitation on the lower limit of the glass transition temperature of the urethane resin. The glass transition temperature of the urethane resin is preferably −65 ° C. or higher, more preferably −55 ° C. or higher, still more preferably −45 ° C. or higher. The glass transition temperature can be measured according to a known method, and can be measured, for example, by using a thermal analyzer such as a differential scanning calorimeter (DSC).

The type of urethane resin is not particularly limited as long as the glass transition temperature is within the above range. The urethane resin is preferably a urethane resin using a non-yellowing polyisocyanate compound and a carbonate polyol compound as monomers (that is, a polymer of a non-yellowing polyisocyanate compound and a carbonate polyol compound). Examples of such urethane resins include Superflex 420, 420NS, 460, 460S, 470, 650 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

The volume average particle size of the resin fine particles (E) is not particularly limited, but is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and even more preferably 10 to 50 nm. The volume average particle size can be obtained by using, for example, a particle size distribution measuring device.

If the content of the resin fine particles (E) is too small, the effect of improving the transfer quality cannot be sufficiently obtained. Therefore, the content of the resin fine particles (E) in the water-based inkjet ink is 2.5% by mass or more, preferably 3.0% by mass or more, and more preferably 3.5 as the solid content (solid content concentration). It is mass% or more. On the other hand, the content of the resin fine particles (E) in the water-based inkjet ink is not particularly limited, but is preferably 15% by mass or less, more preferably 12% by mass or less.

The mass ratio of the pigment (B) to the resin fine particles (E) (pigment (B) / resin fine particles (E)) is not particularly limited, but as the mass ratio increases, the transfer quality improving effect tends to decrease. Therefore, the mass ratio (pigment (B) / resin fine particles (E)) is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.

[Film substrate]
As the film base material, a known transfer film base material used in the transfer printing method for cloth may be used. The film base material may have a single-layer structure consisting of only the base film, or may have a multi-layer structure in which other layers are formed on the base film. The film substrate preferably has a multi-layer structure having a base film and a release coat layer.

Examples of the base film include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film; polyolefin films such as polypropylene film and polyethylene film; cellulose films such as diacetyl cellulose film and triacetyl cellulose film. Examples thereof include a polyurethane film; a polyamide film; a polyimide film; a polyacrylate film; a polymethacrylate film; and a resin film such as a polycarbonate film. From the viewpoint of excellent transfer quality and high color development, a polyester-based film is preferable, and a polyethylene terephthalate film is more preferable. On the other hand, a polyolefin-based film and a polyurethane-based film are preferable because the film follows the unevenness of the mesh of the fibers of the fabric and high fixability can be obtained. Therefore, advantageously, the film substrate comprises a polyester-based film, a polyolefin-based film, or a polyurethane-based film.

The release coat layer may be the same as the release coat layer of a known multi-layer structure transfer film. The release coat layer may be a silicone layer or a non-silicone layer.

When the film substrate has a multi-layer structure, it may have a layer other than the base film and the release coat layer. An example thereof is an antistatic treatment layer.

A transfer film is produced by ejecting the above-mentioned aqueous inkjet ink onto such a film substrate by an inkjet method using an inkjet recording device and drying the ejected aqueous inkjet ink to form a print layer. can do. At this time, it is preferable to preheat the film substrate. As the inkjet recording device, a known inkjet recording device may be used.

Preheating can be performed, for example, by heating the film substrate with the preheater using an inkjet recording device equipped with a preheater. Alternatively, it can be performed by heating the film substrate with a heater independent of the inkjet recording device. This heating is preferably performed so that the temperature of the film substrate is 35 ° C. or higher and 45 ° C. or lower. By performing preheating, the quality of the image formed on the film substrate can be further improved.

The water-based inkjet ink ejection can be performed by ejecting the water-based inkjet ink onto the surface of the film substrate from the inkjet head of the inkjet recording device according to a known method.

Drying can be performed by heating the ejected water-based inkjet ink using, for example, a heating device such as a heater or a hot plate. If the solvent contained in the water-based inkjet ink remains on the print layer, the remaining solvent may volatilize and the transfer quality may be lowered when the transfer film is heated for transfer to the transfer target. Therefore, the drying temperature is preferably 60 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 100 ° C. or lower. The drying time may be appropriately set according to the drying temperature, and is, for example, 5 minutes or more and 60 minutes or less.

[Transfer film]
As described above, a print layer having excellent color development property can be formed to produce a transfer film, and this print layer has excellent bending resistance and adhesiveness to a cloth, and has excellent transfer quality. Can be transferred to fabric. According to this transfer film, only the print layer is transferred to the fabric, so that the texture of the fabric is not easily impaired.

The transfer film comprises a printing layer formed directly on the film substrate. That is, the transfer film includes a film base material and a printing layer in contact with the film base material. Therefore, this transfer fill does not have an intermediate layer (eg, ink receiving layer, thermal transfer layer, adhesive layer, etc.) between the base material and the printing layer. Therefore, the transfer film typically comprises only a film substrate and a printing layer. However, the transfer film may be provided with a release liner or the like for the purpose of protecting the print layer.

<Pretreatment liquid application process>
The method for producing a decorative product according to the present invention further includes a step of applying a pretreatment liquid containing at least water (A') to the surface to be transferred of the fabric (pretreatment liquid application step) before the transfer step. Is preferable. The transfer quality can be improved by performing the pretreatment liquid application step. In particular, when the material of the cloth has a hydrophilic group (for example, when the material of the cloth is cotton), the urethane resin constituting the resin fine particles (E) is made of the material of the cloth by van der Waals force or hydrogen bonding. When the material of the fabric does not have a hydrophilic group (eg, when the material of the fabric is a polyester material), it is easy to bind to the constituent molecules, the printed layer has adhesiveness to the fabric, and the transfer quality is likely to be high. When the material of the cloth is cotton but the cloth is dyed and the hydrophilic groups are consumed), it is difficult for the printed layer to obtain adhesiveness to the cloth, and the transfer quality tends to be deteriorated. However, the water contained in the pretreatment liquid is vaporized by heating during transfer and is retained between the constituent molecules of the material of the fabric, so that the adhesiveness of the print layer to the fabric is improved. Therefore, when the material of the fabric does not have a hydrophilic group, the transfer quality can be remarkably improved. In addition, the water contained in the pretreatment liquid is vaporized by heating during transfer, so that the film substrate of the transfer film can be prevented from being fused to the fabric during transfer.

The material of the fabric is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool; synthetic fibers such as polyester, polypropylene, polyamide, acetate, triacetate, and polyurethane; and biodecomposition of polylactic acid and the like. Sex fibers; and blended fibers thereof and the like. The form of the cloth is not particularly limited, and may be a woven fabric, a knitted fabric, a non-woven fabric, or the like. The cloth is, for example, a cloth for clothing such as T-shirts, polo shirts, and jeans.

The water (A') used in the pretreatment liquid is the same as the water (A) used in the water-based inkjet ink. The pretreatment liquid contains only water (A') as an example, but may contain other components (eg, water-soluble organic solvent, surfactant, resin fine particles, cross-linking agent, etc.). The resin fine particles and the cross-linking agent which may be contained in the pretreatment liquid are the same as those used in the post-treatment liquid described later.

The pretreatment liquid is applied, for example, by spraying the pretreatment liquid onto the fabric; applying the pretreatment liquid to the fabric by an inkjet method; and applying the pretreatment liquid to the fabric using a coater such as a roll coater. The pretreatment liquid can be applied to the cloth using a spatula or the like; the cloth can be dipped in the pretreatment liquid or the like. Among them, the method of spray-spraying the pretreatment liquid and applying it to the fabric and the method of applying the pretreatment liquid to the fabric by the inkjet method are preferable because they can be easily applied to a desired place, and the pretreatment liquid is spray-sprayed. The method of applying to the cloth is more preferable.

<Transfer process>
The transfer step can be typically performed by laminating the printed layer of the prepared transfer film and the surface to be transferred of the fabric and applying pressure while heating.

The heating temperature is not particularly limited as long as the print layer can be transferred, and is, for example, 125 ° C. or higher, preferably 130 ° C. or higher. On the other hand, the heating temperature is lower than the melting point of the film substrate of the transfer film, for example, 200 ° C. or lower, preferably 185 ° C. or lower. Further, when the heating temperature is equal to or higher than the softening point of the film base material of the transfer film, the film base material can be made to follow the unevenness of the mesh of the fibers of the cloth, and the printed layer transferred by this can be fixed to the cloth. It is advantageous because it can improve the sex. The pressure is not particularly limited as long as the print layer can be transferred, and is, for example, 100 g / cm ² or more and 10 kg / cm ² or less, preferably 200 g / cm ² or more and 5 kg / cm ² or less. The pressurizing time is not particularly limited as long as the print layer can be transferred, and is, for example, 10 seconds or more and 10 minutes or less, preferably 30 seconds or more and 5 minutes or less.

By applying pressure while heating, the print layer is transferred from the transfer film to the surface to be transferred of the fabric, and the fabric provided with the print layer is obtained as a decorative product.

<Fixing process>
In the method for producing a decorative product according to the present invention, at least water (A ″) and resin fine particles (F) are added to the transferred surface of the fabric to which the print layer is transferred after the step of transferring the print layer. It is preferable to further include a step (fixing step) of applying and heating the post-treatment liquid containing the mixture. By performing the fixing step, it is possible to impart excellent fixing property to the fabric to the transferred print layer.

The water (A ″) contained in the post-treatment liquid is the same as the water (A) used in the water-based inkjet ink.

As the resin fine particles (F) contained in the post-treatment liquid, for example, resin fine particles generally used as a fixing resin in an aqueous inkjet ink can be used. Examples of resins constituting the resin fine particles include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, polyethylene resin, polypropylene resin, fluoroolefin resin, butadiene resin, styrene resin, styrene-butadiene resin, and styrene-acrylic resin. Examples thereof include ethylene-acrylic resin, vinyl chloride resin, and acrylic-silicone resin. The resin fine particles are preferably urethane resin fine particles, more preferably urethane resin fine particles having a glass transition temperature (Tg) of 0 ° C. or lower, and further preferably the above-mentioned aqueous solution used for forming a print layer of a transfer film. It is the same resin fine particles as the resin fine particles (E) contained in the inkjet ink.

The resin fine particles (F) do not have to be made of one kind of resin, and may be made of two or more kinds of resins. For example, core-shell type resin fine particles having different resin compositions in the core part and the shell part, and acrylic fine particles (seed particles) prepared in advance to control the particle size are further emulsified with different types of monomers. Fine particles obtained by polymerization can be used. Further, hybrid type resin fine particles obtained by chemically binding resin fine particles composed of different resins, such as fine particles made of acrylic resin and fine particles made of urethane resin, can be used.

The content of the resin fine particles (F) in the post-treatment liquid is not particularly limited, but is preferably 0.05% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less. ..

The post-treatment liquid may contain components other than water (A ″) and resin fine particles (F). Examples of the component include a cross-linking agent (G), a surfactant, a water-soluble organic solvent and the like.

It is advantageous that the post-treatment liquid contains a cross-linking agent (G) because it can suppress discoloration (particularly whitening) other than the transfer portion of the surface to be transferred of the fabric. The cross-linking agent (G) is a component that cross-links the resin of the resin fine particles (F) contained in the post-treatment liquid, and the type thereof may be appropriately selected according to the resin type of the resin fine particles (F). When the resin fine particles (F) are urethane resins, for example, a carbodiimide compound can be used as the cross-linking agent (G).

The carbodiimide compound is a compound having a carbodiimide group (-N = C = N-). The carbodiimide compound is preferably a polycarbodiimide resin. The carbodiimide compound preferably has a hydrophilic group (eg, a polyoxyalkylene group) and is preferably water-soluble or capable of forming an aqueous emulsion.

As the carbodiimide compound, for example, the polycarbodiimide described in Japanese Patent No. 6291621 can be used. It is also available as a commercial product, and examples of commercial products include Carbodilite V-02, V-02-L2, SV-02, V-04, V-10, E-02, E-03A, and E. -05 (above, manufactured by Nisshinbo Chemical Co., Ltd.) and the like can be mentioned.

The content of the carbodiimide compound in the post-treatment liquid is not particularly limited, but is preferably 0.01% by mass or more and 2% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less.

The mass ratio of the cross-linking agent (G) to the resin fine particles (F) is preferably 0.001 or more and 0.2 or less, and more preferably 0.005 or more and 0.10 or less. At this time, discoloration (particularly browning) other than the transfer portion of the surface to be transferred of the fabric can be further suppressed. In addition, the print layer can be made stronger, and stickiness of the print layer can be suppressed.

The post-treatment liquid is applied, for example, by spraying the post-treatment liquid onto the fabric; applying the post-treatment liquid to the fabric by an inkjet method; and applying the post-treatment liquid to the fabric using a coater such as a roll coater. The post-treatment liquid is applied to the cloth using a spatula or the like; the cloth can be dipped in the post-treatment liquid or the like. Among them, the method of spray-spraying the post-treatment liquid and applying it to the cloth and the method of applying the post-treatment liquid to the cloth by the inkjet method are preferable because it can be easily applied to a desired place, and the post-treatment liquid is spray-sprayed. The method of applying to the cloth is more preferable.

The heating temperature is not particularly limited, and is, for example, 125 ° C. or higher, preferably 130 ° C. or higher. On the other hand, the heating temperature is, for example, 200 ° C. or lower, preferably 185 ° C. or lower, and the heating time is not particularly limited, and is, for example, 10 seconds or more and 10 minutes or less, preferably 20 seconds or more and 5 minutes or less.

In a preferred embodiment (a) of the pretreatment liquid and the posttreatment liquid, the pretreatment liquid (a) and the posttreatment liquid (a) are water (Aa), a carboxylate anion, and a monovalent cation, respectively. It contains urethane resin fine particles (Fa) and a surfactant (HA).

This preferred aspect (a) is particularly suitable when the material of the cloth is cotton, and the transferability of the print layer of the transfer film and the washing fastness of the transferred print layer are improved with respect to the cloth of the cotton material. Especially excellent. Further, in this preferred embodiment, it is highly suppressed that the texture of the cotton material fabric is impaired by the transferred printing layer.

The water (Aa) is the same as the water (A) used for the water-based inkjet ink. The content of water (Aa) in each of the treatment liquid (a) and the post-treatment liquid (a) is not particularly limited, but is preferably 85% by mass or more, and preferably 90% by mass or more.

The carboxylate anion is an anion in which H ⁺ is dissociated from a monovalent or polyvalent carboxylic acid compound. Examples of the carboxylic acid compound include monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and lactic acid; Divalent carboxylic acids such as malic acid; trivalent carboxylic acids such as citric acid and the like can be mentioned. Of these, acids that can be used in foods (eg, acetic acid, succinic acid, citric acid, etc.) are preferable from the viewpoint of safety. Examples of the monovalent cation include alkali metal cations such as potassium ion (K ⁺ ) and sodium ion (Na ⁺ ). The carboxylate anion is hydrogen-bonded to the urethane resin fine particles (Fa), and when the carboxylate anion is a divalent or higher anion, the urethane resin fine particles (Fa) can be crosslinked. Therefore, the carboxylic acid compound is preferably divalent or higher. As the carboxylic acid compound, succinic acid and citric acid are more preferable, and citric acid is further preferable.

The contents of the carboxylate anion and the monovalent cation in each of the treatment liquid (a) and the post-treatment liquid (a) are not particularly limited. The higher the content of these, the better the transferability tends to be, but if the content is too high, the fabric may turn brown. The content of each of the treatment liquid (a) and the post-treatment liquid (a) is preferably 0.05% by mass or 1.0% by mass, more preferably 0. It is 1% by mass or more and 0.6% by mass or less, and more preferably 0.1% by mass or more and 0.4% by mass or less.

The carboxylate anion and the monovalent cation may be obtained by dissolving a carboxylate or a hydrate thereof in the pretreatment liquid (a) and the post-treatment liquid (a), or the pretreatment liquid (a). And the post-treatment liquid (a) may be prepared by dissolving a salt containing a carboxylic acid and a monovalent cation.

Since the pretreatment liquid (a) and the posttreatment liquid (a) contain a carboxylate anion and a monovalent cation, respectively, the pH in these liquids can be in the weak alkaline range. The pH of the pretreatment liquid (a) and the post-treatment liquid (a) is preferably 8 or more and less than 11, respectively.

The urethane resin fine particles (Fa) are not particularly limited, but known urethane resin fine particles used as a fixing resin for an aqueous inkjet ink can be used. The urethane resin fine particles (Fa) preferably have a Tg of 0 ° C. or lower, and more preferably a Tg of −10 ° C. or lower. The content of the urethane resin fine particles (FA) in each of the pretreatment liquid (a) and the post-treatment liquid (a) is not particularly limited, but if it is too small, the washing fastness tends to decrease, and it is too large. And the effect of suppressing the reduction of the texture of the fabric may be reduced. The content of the urethane resin fine particles (Fa) is preferably 1.5% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 7% by mass or less.

The surfactant (HA) is not particularly limited, but a silicone-based surfactant is preferable, and specific examples thereof are the same as those of the silicone-based surfactant (D). The content of the surfactant (HA) in each of the pretreatment liquid (a) and the post-treatment liquid (a) is not particularly limited, but is preferably 0.05% by mass or more and 5.0% by mass or less. Yes, more preferably 0.1% by mass or more and 1.0% by mass or less.

The pretreatment liquid (a) and the post-treatment liquid (a) may contain other components as long as the effects of the present invention are not significantly impaired.

In a preferred embodiment (a), the compositions of the pretreatment liquid (a) and the posttreatment liquid (a) may be the same or different, and one liquid agent may be used as the pretreatment liquid (a) and the posttreatment liquid (a). It is preferable that they are the same because they can be used for both the liquid (a).

In a preferred embodiment (b) of the pretreatment liquid and the posttreatment liquid, the pretreatment liquid (b) and the posttreatment liquid (b) are water (Ab), urethane resin fine particles (Fb), and urethane resin fine particles (Fb), respectively. Contains a surfactant (Hb). The pretreatment liquid (b) and the post-treatment liquid (b) may further contain a carbodiimide-based cross-linking agent (G-b).

This preferred aspect (b) is particularly suitable when the material of the cloth is polyester, and the transferability of the print layer of the transfer film and the washing fastness of the transferred print layer are improved with respect to the cloth of the polyester material. Especially excellent. Further, in this preferred embodiment, it is highly suppressed that the texture of the polyester material fabric is impaired by the transferred printing layer.

The water (Ab) is the same as the water (A) used for the water-based inkjet ink. The content of water (Ab) in each of the treatment liquid (b) and the post-treatment liquid (b) is not particularly limited, but is preferably 85% by mass or more, and preferably 90% by mass or more.

As the carbodiimide-based cross-linking agent (G-b), the carbodiimide compound used as the above-mentioned cross-linking agent (G) can be preferably used. The carbodiimide-based cross-linking agent (G-b) is a cross-linking agent for urethane resin fine particles (F-b), but polyester can also be cross-linked, and is a component that further improves washing fastness. The content of the carbodiimide-based cross-linking agent (G-b) in each of the pre-treatment liquid (b) and the post-treatment liquid (b) is not particularly limited, but if it is too small, the urethane resin fine particles (F-b) may be cross-linked. It may be insufficient, and if it is too much, the effect of suppressing the reduction of the texture of the fabric may be reduced. The content of the carbodiimide-based cross-linking agent (Gb) is preferably 0.05% by mass or more and 1.5% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less.

The urethane resin fine particles (Fb) are not particularly limited, but known urethane resin fine particles used as a fixing resin for an aqueous inkjet ink can be used. The urethane resin fine particles (Fb) preferably have a Tg of 0 ° C. or lower, and more preferably a Tg of −10 ° C. or lower. The content of the urethane resin fine particles (F-b) in each of the pretreatment liquid (b) and the post-treatment liquid (b) is not particularly limited, but if it is too small, the washing fastness tends to decrease, and it is too large. And the effect of suppressing the reduction of the texture of the fabric may be reduced. The content of the urethane resin fine particles (Fb) is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 0.7% by mass or more and 7% by mass or less.

The ratio of the carbodiimide-based cross-linking agent (Gb) to the urethane resin fine particles (Fb) (carbodiimide-based cross-linking agent (Gb) / urethane resin fine particles (Fb)) is not particularly limited, but is 1% by mass. 50% by mass or more is preferable, and 1% by mass or more and 20% by mass or less is more preferable.

The surfactant (Hb) is not particularly limited, but a silicone-based surfactant is preferable, and specific examples thereof are the same as those of the silicone-based surfactant (D). The content of the surfactant (H-b) in each of the pretreatment liquid (b) and the post-treatment liquid (b) is not particularly limited, but is preferably 0.05% by mass or more and 5.0% by mass or less. Yes, more preferably 0.1% by mass or more and 1.0% by mass or less.

The pretreatment liquid (b) and the post-treatment liquid (b) may contain other components as long as the effects of the present invention are not significantly impaired.

In a preferred embodiment (b), the compositions of the pretreatment liquid (b) and the posttreatment liquid (b) may be the same or different, and one liquid agent may be used as the pretreatment liquid (b) and the posttreatment liquid (b). It is preferable that they are the same because they can be used for both the liquid (b).

In another preferred embodiment (c) of the pretreatment and post-treatment liquids, the pretreatment liquid is water (A-c1); a combination of carboxylate anion and monovalent cation, and a detergent (G-c). Either or both; urethane resin fine particles (F-c1); and surfactant (H-c1) are contained, and the post-treatment liquid is water (A-c2), acrylic resin fine particles (F-c2), and Contains a surfactant (H-c2).

In this preferred aspect (c), it is suitable whether the material of the cloth is polyester or cotton, and the transferability of the print layer of the transfer film and the transferred printing are performed on the cotton material and the cloth made of the polyester material. Especially excellent in the washing fastness of the layer. Further, in this preferred embodiment, it is suppressed that the texture of the cotton material and the polyester material fabric is impaired by the transferred printing layer. In addition, the transferred print layer is suppressed from being re-transferred to the fabric or another print layer.

The water (A-c1) is the same as the water (A) used for the water-based inkjet ink. The content of water (A-c1) in the pretreatment liquid (c) is not particularly limited, but is preferably 85% by mass or more, and preferably 90% by mass or more.

The pretreatment liquid (c) contains a combination of a carboxylate anion and a monovalent cation, a carbodiimide-based cross-linking agent (G-c1), or a combination of a carboxylate anion and a monovalent cation and a carbodiimide. Contains both with a system cross-linking agent (G-c).

The carboxylate anion and the monovalent cation are the same as the carboxylate anion and the monovalent cation used in the pretreatment liquid (a) and the post-treatment liquid (a). The content of these in the pretreatment liquid (c) is not particularly limited, but is preferably 0.05% by mass or less, and more preferably 0.1% by mass in terms of these carboxylates. It is 0.6% by mass or less, and more preferably 0.1% by mass or more and 0.4% by mass or less.

As the carbodiimide-based cross-linking agent (G-c), the carbodiimide compound used as the above-mentioned cross-linking agent (G) can be preferably used. The content of the carbodiimide-based cross-linking agent (G-c) in the pretreatment liquid (c) is not particularly limited, but if it is too small, the cross-linking of the urethane resin fine particles (F-c) may be insufficient. If it is too much, the effect of suppressing the reduction of the texture of the fabric may be reduced. The content of the carbodiimide-based cross-linking agent (G-c) is preferably 0.05% by mass or more and 1.5% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less.

The urethane resin fine particles (F-c1) are not particularly limited, but known urethane resin fine particles used as a fixing resin for an aqueous inkjet ink can be used. The urethane resin fine particles (F—c1) preferably have a Tg of 0 ° C. or lower, and more preferably a Tg of −10 ° C. or lower. The content of the urethane resin fine particles (F-c1) in the pretreatment liquid (c) is not particularly limited, but if it is too small, the washing fastness tends to decrease, and if it is too large, the effect of suppressing the texture reduction of the fabric is small. There is a risk of becoming. The content of the urethane resin fine particles (F-c1) is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 12% by mass or less.

The surfactant (H-c1) is not particularly limited, but a silicone-based surfactant is preferable, and specific examples thereof are the same as those of the silicone-based surfactant (D). The content of the surfactant (H-c1) in the pretreatment liquid (c) is not particularly limited, but is preferably 0.05% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass. % Or more and 1.0 mass or less.

The water (A-c2) is the same as the water (A) used for the water-based inkjet ink. The content of water (A-c2) in the post-treatment liquid (c) is not particularly limited, but is preferably 85% by mass or more, and preferably 90% by mass or more.

As the acrylic resin fine particles (F-c2), known acrylic resin fine particles used as a fixing resin for water-based inkjet ink can be used. The acrylic resin fine particles may be fine particles of a homopolymer of an acrylic monomer (particularly acrylic acid ester), and may be a copolymer (for example, styrene-acrylic acid ester) in which an acrylic monomer (particularly acrylic acid ester) is copolymerized. It may be fine particles of (copolymer, etc.). The acrylic resin fine particles (F-c2) can be synthesized according to a known method, and can also be obtained as a commercially available product in the form of an emulsion. Examples of commercially available products include Movinyl 6960, 6963, 6718, 6751D, 6750, 6760, 6770, 6901, 6951, 6940, 6950 and the like manufactured by Japan Coating Resin Co., Ltd. As the acrylic resin fine particles (F—c2), those having a Tg of 0 ° C. or lower are preferable, and those having a Tg of −10 ° C. or lower are more preferable.

The content of the acrylic resin fine particles (F-c2) in the post-treatment liquid (c) is not particularly limited, but if it is too small, the maximum transfer suppressing effect tends to decrease, and if it is too large, the washing fastness improving effect may be reduced. There is. The content of the acrylic resin fine particles (F-c2) in the post-treatment liquid (c) is preferably 1% by mass or more and 18% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and further preferably. It is 2% by mass or more and 7% by mass or less.

The post-treatment liquid (c) preferably further contains urethane resin fine particles. When the post-treatment liquid (c) contains urethane resin fine particles in addition to the acrylic resin fine particles (F-c2), the washing fastness is further improved. The content of the urethane resin fine particles in the post-treatment liquid (c) is not particularly limited, but is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 7% by mass or less.

The surfactant (H-c2) is not particularly limited, but a silicone-based surfactant is preferable, and specific examples thereof are the same as those of the silicone-based surfactant (D). The content of the surfactant (H-c2) in the pretreatment liquid (c) is not particularly limited, but is preferably 0.05% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass. % Or more and 1.0 mass or less.

The pretreatment liquid (c) and the post-treatment liquid (c) may contain other components as long as the effects of the present invention are not significantly impaired.

As described above, it is possible to obtain a decorative product in which the fabric is printed. Since the transfer film that can be produced by the inkjet method is used in the production method of the present invention, it is possible to print various designs on a cloth in a small amount on demand. Further, since the print layer of the transfer film is formed by the water-based inkjet ink having a specific composition, the color development property is high. Further, the print layer formed by the water-based inkjet ink having a specific composition can transfer only the print layer from the film base material of the transfer film to the fabric. Therefore, it is possible to perform printing without impairing the texture of the fabric.

From another point of view, the present invention is a decorative product including a cloth and a printing layer in contact with the cloth, the printing layer being formed by using the above-mentioned water-based inkjet ink, and the printing layer. Is transferred onto the fabric.

Such a decorative product is excellent in color development of the print layer, and the texture of the fabric is hardly or not impaired by the print layer.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

<Examples 1 to 13>
[Preparation of transfer film]
The components shown in Table 1 below are mixed according to a conventional method to prepare cyan (C) ink, magenta (M) ink, yellow (Y) ink, black (K) ink, and white (Wh) ink, and water-based. Obtained an inkjet ink set.

(The numerical value for each component in the table indicates the mass ratio (%).)
CAB-O-JET260C (manufactured by Cabot): Cyan-based self-dispersing pigment (aqueous emulsion with a solid content of 10% by mass)
CAB-O-JET260M (manufactured by Cabot): Magenta self-dispersing pigment (aqueous emulsion with a solid content of 10% by mass)
CAB-O-JET270 (manufactured by Cabot): Yellow self-dispersing pigment (aqueous emulsion with a solid content of 10% by mass)
CAB-O-JET300 (manufactured by Cabot): Black self-dispersing pigment (aqueous emulsion with a solid content of 15% by mass)
WD-0024 (manufactured by TAYCA): Titanium oxide (aqueous emulsion with a solid content of 45%)
SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.): Silicone-based surfactant "Silface SAG503A"
Superflex 460 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Aqueous emulsion of urethane resin (resin Tg: -21 ° C, solid content 38% by mass)

The following were prepared as the film base material of the transfer film.
Film base material 1: Panac polyethylene terephthalate mold release / transfer film "TP-01"
Film base material 2: Toray Industries, Inc. olefin release film "DECOFIT"

The water-based inkjet ink set shown in Table 1 is Roland D. Gee. It was installed in the inkjet printer "VS-3000i" manufactured by the same company. The temperature of the preheater of this printer was set to 45 ° C., and printing was performed on the film base material 1 or the film base material 2 described above. The printed film substrate was dried on a hot plate set at 100 ° C. for 30 minutes to obtain a transfer film having a printing layer on the film substrate. The image of the print layer is a solid image of five colors of C, M, Y, K, and Wh, and the size is 40 mm × 40 mm ×.

As fabric products, 100% cotton white T-shirt (Cab's "United Athel 5.6 oz high quality T-shirt"), 100% cotton black T-shirt (TOMS's "Printstar 6.6 ounce high grade T-shirt") , And a 100% polyester white T-shirt (“United Athel 4.1 oz dry athletic T-shirt” manufactured by Cab) was prepared.

In some examples, as a pretreatment liquid application step, water was spray-coated on the surface to be transferred of these T-shirts as a pretreatment liquid.

In the flat sublimation transfer press device "HSP-5400" manufactured by Hashima Co., Ltd., the T-shirt and the transfer film were superposed so that the printed layer of the transfer film was in contact with the surface to be transferred of these T-shirts. Further, silicon paper and a rubber plate were placed on it. The print layer was transferred from the transfer film to the T-shirt by hot pressing with this press device at the temperature shown in Table 2 and a pressure of about 300 g / cm ² for 60 seconds.

The following evaluation was performed on the decorative product in which the print layer was transferred to the fabric product (T-shirt) obtained by the above method.

[Transfer quality]
The state of the printed layer was visually observed and the transfer quality was evaluated according to the following criteria. The results are shown in Tables 2 and 3. In addition, "○" and "△" were accepted.
〇: The entire print layer is in close contact with the T-shirt △: Part of the print layer on the T-shirt is floating ×: The print layer cannot be transferred, only a part of the print layer is transferred, Or the film is fused and does not come off

[Color development]
The printed layer on the T-shirt was visually observed, and the color development property was evaluated according to the following criteria. The results are shown in Tables 2 and 3. In addition, "○" and "△" were accepted.
〇: The print layer can be transferred to the color without shading, and the print layer does not remain on the transfer film base material. Δ: The print layer can be transferred without shading to the color, but the print layer can be seen on the transfer film base material. ×: The print layer remains thick on the transfer film substrate, and the color density of the transferred print layer shows shading.

[Fixability]
A cloth moistened with water was prepared, the cloth was rubbed against the print layer on the T-shirt, and whether or not a part of the print layer was detached was visually observed, and the fixability was evaluated according to the following criteria. Further, in the example in which the fixing property was poor, a post-treatment liquid was spray-coated on the surface to be transferred of the T-shirt as a fixing step. Silicon paper was placed on it, and it was heated at 150 ° C. for 60 seconds without pressurization using the above press device, and the fixability thereafter was evaluated. The post-treatment liquid contains 94.8% by mass of water, 0.2% by mass of SAG503A (silicone-based surfactant), and 5% by mass of Superflex 460 (emulsion containing 38% by mass of urethane resin fine particles). I used what I did. The results are shown in Tables 2 and 3. In addition, "○" was accepted.
〇: The print layer is not detached ×: The print layer is partially detached

As shown in the results of Tables 2 and 3, it can be seen that high color development can be obtained by producing a transfer film using an inkjet ink having a specific composition and transferring it to a cloth. Further, in Examples 1 to 13, since only the print layer was transferred to the fabric as a single layer, the texture of the fabric was not impaired. Further, from the results in Table 2, it can be seen that the transfer quality is improved by performing the pretreatment liquid application step. Further, from the results of Tables 2 and 3, it can be seen that the fixing property is improved by performing the fixing step.

Furthermore, the present inventor examined the composition of the water-based inkjet ink, and confirmed that the color-developing property was high when the content of the substituted butanol in the ink was 9% by mass or more and 27% by mass or less. Further, it was confirmed that the print layer can be transferred as a single layer when the content of the resin fine particles (E) in the ink is 2.5% by mass or more.

[Examples 14 to 17 and Reference Examples 1 to 3]
A treatment liquid having the composition shown in Table 4 was prepared. On the other hand, a transfer film was produced in the same manner as above using the above-mentioned water-based inkjet ink set and the film substrate 1 (polyethylene terephthalate release / transfer film "TP-01" manufactured by Panac Co., Ltd.). The 100% cotton white T-shirt was prepared, and the prepared treatment liquid was spray-coated on the surface to be transferred of the T-shirt. In the flat sublimation transfer press device "HSP-5400" manufactured by Hashima Co., Ltd., the T-shirt and the transfer film were overlapped so that the printed layer of the transfer film was in contact with the transferred surface of the 100% cotton white T-shirt. .. Furthermore, silicon paper and a rubber plate were placed on it. The print layer was transferred from the transfer film to the T-shirt by hot pressing at 150 ° C. at a pressure of about 300 g / cm ² for 20 seconds using this press device.

The treatment liquid prepared above was spray-coated on the area including the print layer on the surface to be transferred of the T-shirt. Silicone paper was placed on it, and it was heated at 150 ° C. for 60 seconds without pressurization using the above press device. In this way, a T-shirt with a printed layer transferred was obtained.

The fixability, white blur, browning, and stickiness of the T-shirt to which the printed layer was transferred were evaluated as follows. The results are shown in Table 4.

[Fixability]
The printed layer transferred to the T-shirt was rubbed with a nail, and whether or not the printed layer was peeled off was visually observed and evaluated according to the following criteria.
〇: The print layer does not peel off ×: Peeling occurs on a part of the print layer

[White bokeh]
Whether or not whitening occurred in the fabric of the non-transferred portion of the transferred surface of the T-shirt was visually observed and evaluated according to the following criteria.
〇: The fabric is not whitish △: The fabric is slightly whitish ×: The fabric is whitish

[Browning]
Whether or not browning occurred in the fabric of the non-transferred portion of the transferred surface of the T-shirt was visually observed and evaluated according to the following criteria.
〇: The fabric is not brownish △: The fabric is slightly brownish at the boundary with the transfer film ×: The fabric is brownish at the boundary with the transfer film

[Sticky]
Whether or not the surface of the printed layer transferred to the T-shirt was sticky was confirmed by touching it with a finger, and evaluated according to the following criteria.
〇: The surface of the print layer is not sticky △: The surface of the print layer is slightly sticky ×: The surface of the print layer is sticky

(The numerical value for each component in the table indicates the mass ratio (%).)
V-04 (manufactured by Nisshinbo Chemical Co., Ltd.): Water-soluble polycarbodiimide resin aqueous solution "carbodilite V-04" (solid content 40% by mass)
Urethane resin emulsion: Superflex 460 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., resin Tg: -21 ° C, solid content 38% by mass)

From the results in Table 4 (particularly, comparison between Examples 14 to 16 and Reference Examples 1 to 3), it can be seen that the fixability can be improved by containing at least water and resin fine particles in the post-treatment liquid. From the comparison between Examples 14 and Examples 15 and 16, it can be seen that the post-treatment liquid further contains a cross-linking agent, so that whitening of the surface to be transferred of the fabric other than the transfer portion can be suppressed. Further, by comparing Example 15 and Example 16, by adjusting the mass ratio of the cross-linking agent to the resin fine particles contained in the post-treatment liquid, it is possible to suppress browning of the surface to be transferred of the fabric other than the transfer portion. It can be seen that the stickiness of the print layer can be suppressed.

[Examples 18 to 28]
The water-based inkjet ink set shown in Table 1 is Roland D. Gee. It was installed in the inkjet printer "VS-3000i" manufactured by the same company. The temperature of the preheater of this printer was set to 40 ° C., and printing was performed on a film substrate (polyethylene terephthalate mold release / transfer film "TP-05" manufactured by Panac Co., Ltd.). At this time, W was overlaid on the full solid layer of CMYK and printed. The printed film substrate was dried on a hot plate set at 100 ° C. for 3 minutes to obtain a transfer film having a printing layer on the film substrate. The size of the transfer film was 160 mm × 160 mm ×.

A treatment liquid having the composition shown in Table 5 was prepared and filled in a handy spray. A 100% cotton white T-shirt (“United Athel 5.6 oz high quality T-shirt 5100” manufactured by Cab) was prepared, and the treatment liquid prepared above was spray-coated on the surface to be transferred of this T-shirt. The coating amount of the treatment liquid was 0.010 to 0.015 g / cm ² . In the flat sublimation transfer press device "HSP-5400" manufactured by Hashima Co., Ltd., the T-shirt and the transfer film were superposed so that the printed layer of the transfer film was in contact with the surface to be transferred of the T-shirt. Furthermore, silicon paper and a rubber plate were placed on it. The printing layer was transferred from the transfer film to the T-shirt by hot pressing at 180 ° C. at a pressure of about 300 g / cm ² for 1 minute using this press device.

The treatment liquid prepared above was spray-coated on the area including the print layer on the surface to be transferred of the T-shirt. Therefore, in the examples, the same pretreatment liquid and posttreatment liquid were used. The coating amount of the treatment liquid was 0.010 to 0.015 g / cm ² . Silicone paper was placed on it, and heat pressing was performed at 180 ° C. at a pressure of about 300 g / cm ² for 1 minute using the above press device to fix the print layer. In this way, a T-shirt with a printed layer transferred was obtained.

The T-shirts to which the printed layer was transferred were evaluated for transferability, maintenance of texture, and washing fastness as follows. The results are shown in Table 5.

[Transcribability]
When the print layer was transferred from the transfer film to the T-shirt, it was evaluated whether or not all of the print layer was transferred to the T-shirt.
〇: The entire surface of the print layer is transferred ×: Part or the entire surface of the print layer is not transferred

[Maintaining texture]
When wearing a T-shirt to which the printed layer was transferred, it was evaluated whether or not the stretch of the T-shirt fabric felt uncomfortable. In addition, the presence or absence of yellowing of the T-shirt fabric was evaluated for those that did not feel any discomfort. Based on this, the maintenance of texture was evaluated according to the following criteria.
〇: I do not feel any discomfort △: I feel a little discomfort ×: I feel a sense of discomfort ▲: A little yellowing but not noticeable

[Selective robustness]
The T-shirt on which the print layer was transferred was selected 10 times with a household washing machine, and the color difference ΔE before and after washing the full solid layer of CMYK of the print layer was measured. From this color difference ΔE, the selection fastness was evaluated according to the following criteria.
〇: Color difference ΔE is 10 or less Δ: Color difference ΔE is more than 10 and less than 15 ×: Color difference ΔE is 15 or more

(The numerical value for each component in the table indicates the mass ratio (%).)
Superflex 460 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Urethane resin emulsion (resin Tg: -21 ° C, solid content 38% by mass)
ST-053D (manufactured by Ube Industries, Ltd.): Urethane resin emulsion (resin Tg: -20 ° C or less, solid content 30% by mass)
SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.): Silicone-based surfactant "Silface SAG503A"

Further, in Table 5, the pH range was defined as "acidic" for less than 6; "neutral" for 6 or more and less than 8, "weakly alkaline" for 8 or more and less than 11, and "alkaline" for 11 or more.

From the results in Table 5 (particularly comparison between Examples 18 to 25 and Examples 26 to 28), the material of the fabric is cotton, and the pretreatment liquid and the posttreatment liquid are water, carboxylate anion, and monovalent, respectively. It can be seen that when cations, urethane resin fine particles, and a surfactant are contained, not only high transferability and maintenance of texture but also high washing fastness can be obtained.

[Examples 29 to 37]
The water-based inkjet ink set shown in Table 1 is Roland D. Gee. It was installed in the inkjet printer "VS-3000i" manufactured by the same company. The temperature of the preheater of this printer was set to 40 ° C., and printing was performed on a film substrate (polyethylene terephthalate mold release / transfer film "TP-05" manufactured by Panac Co., Ltd.). At this time, W was overlaid on the full solid layer of CMYK and printed. The printed film substrate was dried on a hot plate set at 100 ° C. for 3 minutes to obtain a transfer film having a printing layer on the film substrate. The size of the transfer film was 160 mm × 160 mm ×.

A treatment liquid having the composition shown in Table 6 was prepared and filled in a handy spray. A 100% polyester white T-shirt (“United Athle 4.1 oz dry athletic T-shirt” manufactured by Cab) was prepared, and the treatment liquid prepared above was spray-coated on the surface to be transferred of this T-shirt. The coating amount of the treatment liquid was 0.010 to 0.015 g / cm ² . In the flat sublimation transfer press device "HSP-5400" manufactured by Hashima Co., Ltd., the T-shirt and the transfer film were superposed so that the printed layer of the transfer film was in contact with the surface to be transferred of the T-shirt. Furthermore, silicon paper and a rubber plate were placed on it. The printing layer was transferred from the transfer film to the T-shirt by hot pressing at 160 ° C. at a pressure of about 300 g / cm ² for 1 minute using this press device.

The treatment liquid prepared above was spray-coated on the area including the print layer on the surface to be transferred of the T-shirt. Therefore, in the examples, the same pretreatment liquid and posttreatment liquid were used. The coating amount of the treatment liquid was 0.010 to 0.015 g / cm ² . A silicon paper was placed on the silicon paper, and the printing layer was fixed by hot pressing at 160 ° C. at a pressure of about 300 g / cm ² for 1 minute using the above press device. In this way, a T-shirt with a printed layer transferred was obtained.

The T-shirts to which the printed layer was transferred were evaluated for transferability, washing fastness, and maintenance of texture as follows. The results are shown in Table 6.

[Transcribability]
When the print layer was transferred from the transfer film to the T-shirt, it was evaluated whether or not all of the print layer was transferred to the T-shirt.
〇: The entire surface of the print layer is transferred ×: Part or the entire surface of the print layer is not transferred

[Washing fastness]
The T-shirt on which the print layer was transferred was selected 10 times with a household washing machine, and the color difference ΔE before and after washing the full solid layer of CMYK of the print layer was measured. From this color difference ΔE, the selection fastness was evaluated according to the following criteria.
〇: Color difference ΔE is 10 or less Δ: Color difference ΔE is more than 10 and less than 15 ×: Color difference ΔE is 15 or more

[Maintaining texture]
When wearing a T-shirt to which the printed layer was transferred, it was evaluated whether or not the stretch of the T-shirt fabric felt uncomfortable. Based on this, the maintenance of texture was evaluated according to the following criteria.
〇: I do not feel any discomfort △: I feel a little discomfort ×: I feel discomfort

(The numerical value for each component in the table indicates the mass ratio (%).)
V-02 (manufactured by Nisshinbo Chemical Co., Ltd.): Water-soluble polycarbodiimide resin aqueous solution "carbodilite V-02" (solid content 40% by mass)
E-05 (manufactured by Nisshinbo Chemical Co., Ltd.): Water-soluble polycarbodiimide resin aqueous solution "carbodilite E-05" (solid content 40% by mass)
Superflex 460 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Urethane resin emulsion (resin Tg: -21 ° C, solid content 38% by mass)
ST-053D (manufactured by Ube Industries, Ltd.): Urethane resin emulsion (resin Tg: -20 ° C or less, solid content 30% by mass)
SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.): Silicone-based surfactant "Silface SAG503A"

From the results in Table 6, when the material of the fabric is polyester and the pretreatment liquid and the posttreatment liquid each contain water, urethane resin fine particles, and a surfactant, only high transferability and maintenance of texture are required. It can be seen that high washing fastness can be obtained.

[Examples 38 to 51]
The water-based inkjet ink set shown in Table 1 is Roland D. Gee. It was installed in the inkjet printer "VS-3000i" manufactured by the same company. The temperature of the preheater of this printer was set to 40 ° C., and printing was performed on a film substrate (polyethylene terephthalate mold release / transfer film "TP-05" manufactured by Panac Co., Ltd.). At this time, W was overlaid on the full solid layer of CMYK and printed. The printed film substrate was dried on a hot plate set at 100 ° C. for 3 minutes to obtain a transfer film having a printing layer on the film substrate. The size of the transfer film was 160 mm × 160 mm ×.

A pretreatment liquid having the composition shown in Table 7 and a post-treatment liquid having the composition shown in Table 8 were prepared and filled in a handy spray. 100% cotton white T-shirt (Cab "United Athel 5.6 oz high quality T-shirt 5100") and 100% polyester white T-shirt (Cab "United Athel 4.1 ounce dry athletic T-shirt") are available. Then, the pretreatment liquid shown in Table 9 was spray-coated on the surface to be transferred of these T-shirts. The coating amount of the pretreatment liquid was 0.010 to 0.015 g / cm ² . In the flat sublimation transfer press device "HSP-5400" manufactured by Hashima Co., Ltd., the T-shirt and the transfer film were superposed so that the printed layer of the transfer film was in contact with the surface to be transferred of the T-shirt. Furthermore, silicon paper and a rubber plate were placed on it. With this press device, 100% cotton white T-shirts are hot pressed at 180 ° C. at a pressure of about 300 g / cm ² for 1 minute, and 100% polyester white T-shirts are hot pressed at 160 ° C. at a pressure of about 300 g / cm ² . The print layer was transferred from the transfer film to the T-shirt by hot pressing for 1 minute.

The post-treatment liquid shown in Table 9 was spray-coated on the area including the print layer on the surface to be transferred of the T-shirt. The amount of the post-treatment liquid applied was 0.010 to 0.015 g / cm ² . Silicon paper is placed on it, and using the above press device, heat press is performed at 180 ° C. for 1 minute at a pressure of about 300 g / cm ² for 100% cotton white T-shirts, and for 100% polyester white T-shirts. The printed layer was fixed by hot pressing at 160 ° C. at a pressure of about 300 g / cm ² for 1 minute. In this way, a T-shirt with a printed layer transferred was obtained.

The T-shirts to which the printed layer was transferred were evaluated for transferability, texture maintenance, retransfer inhibition, and washing fastness as follows. The results are shown in Table 9.

[Transcribability]
When the print layer was transferred from the transfer film to the T-shirt, it was evaluated whether or not all of the print layer was transferred to the T-shirt.
〇: The entire surface of the print layer is transferred ×: Part or the entire surface of the print layer is not transferred

[Maintaining texture]
When wearing a T-shirt to which the printed layer was transferred, it was evaluated whether or not the stretch of the T-shirt fabric felt uncomfortable. Based on this, the maintenance of texture was evaluated according to the following criteria.
〇: I do not feel any discomfort △: I feel a little discomfort ×: I feel discomfort

[Retranscription inhibitory property]
Immediately after fixing, the surface to which the printed layer of the T-shirt was transferred was folded, and the presence or absence of peeling of the transferred printed layer was visually observed and evaluated according to the following criteria.
〇: The print layer is not peeled off and retransfer does not occur △: A part of the print layer is peeled off and retransferred to another surface ×: The entire surface of the print layer is peeled off and retransferred to another surface

[Selective robustness]
The T-shirt on which the print layer was transferred was selected 10 times with a household washing machine, and the color difference ΔE before and after washing the full solid layer of CMYK of the print layer was measured. From this color difference ΔE, the selection fastness was evaluated according to the following criteria.
〇: Color difference ΔE is 10 or less Δ: Color difference ΔE is more than 10 and less than 15 ×: Color difference ΔE is 15 or more

(The numerical value for each component in the table indicates the mass ratio (%).)
V-02 (manufactured by Nisshinbo Chemical Co., Ltd.): Water-soluble polycarbodiimide resin aqueous solution "carbodilite V-02" (solid content 40% by mass)
E-05 (manufactured by Nisshinbo Chemical Co., Ltd.): Water-soluble polycarbodiimide resin aqueous solution "carbodilite E-05" (solid content 40% by mass)
Superflex 460 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Urethane resin emulsion (resin Tg: -21 ° C, solid content 38% by mass)
Movinyl 6963 (manufactured by Japan Coating Resin): Styrene-acrylic resin emulsion (resin Tg: -26 ° C, solid content 45% by mass)
Movinyl 6751D (manufactured by Japan Coating Resin): Acrylic resin emulsion (resin Tg: -32 ° C, solid content 50% by mass)
ST-053D (manufactured by Ube Industries, Ltd.): Urethane resin emulsion, resin Tg: -20 ° C or less, solid content 30% by mass)
SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.): Silicone-based surfactant "Silface SAG503A"

From the results in Tables 7-9, the pretreatment liquid contains water; a combination of a carboxylate anion and a monovalent cation, and / or both of a cross-linking agent; urethane resin fine particles; and a surfactant, and is a post-treatment liquid. However, when it contains water, acrylic resin fine particles, and a surfactant, not only high transferability and texture maintenance to cotton and polyester materials, but also high washing fastness and high retransfer suppression property can be obtained. You can see that.

The present invention relates to the manufacture of a decorative product obtained by decorating a fabric by printing, and can cope with small-quantity printing of various designs on demand.

Claims (9)

A water-based inkjet ink containing at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin fine particles (E).
The ink contains 9 parts by mass of at least one substituted butanol selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). % Or more and 27% by mass or less
The resin fine particles (E) are urethane resin fine particles having a glass transition temperature of 0 ° C. or lower.
The content of the resin fine particles (E) in the ink is 2.5% by mass or more.
A process of preparing a transfer film having a printing layer directly formed on a substrate using a water-based inkjet ink, and a process of preparing a transfer film.
A step of bonding the print layer of the transfer film and the surface to be transferred of the fabric to transfer the print layer.
A method of manufacturing a decorative item, including. The production method according to claim 1, further comprising a step of applying a pretreatment liquid containing at least water (A') to the surface to be transferred of the fabric before the step of transferring the print layer. After the step of transferring the print layer, a step of applying a post-treatment liquid containing at least water (A ″) and resin fine particles (F) to the transferred surface of the fabric to which the print layer is transferred and heating the surface. The manufacturing method according to claim 1 or 2, further comprising. The production method according to claim 3, wherein the post-treatment liquid further contains a cross-linking agent. Before the step of transferring the print layer, the pretreatment liquid is applied to the surface to be transferred of the fabric.
After the step of transferring the printed layer, a step of applying a post-treatment liquid to the surface to be transferred of the fabric to which the printed layer is transferred and heating the printed layer is further provided.
The material of the cloth is cotton,
The pretreatment liquid and the post-treatment liquid each contain water (Aa), a carboxylate anion, a monovalent cation, urethane resin fine particles (Fa), and a surfactant (HA). The manufacturing method according to claim 1. Before the step of transferring the print layer, the pretreatment liquid is applied to the surface to be transferred of the fabric.
After the step of transferring the printed layer, a step of applying a post-treatment liquid to the surface to be transferred of the fabric to which the printed layer is transferred and heating the printed layer is further provided.
The material of the fabric is polyester,
The production method according to claim 1, wherein the pretreatment liquid and the post-treatment liquid each contain water (Ab), urethane resin fine particles (Fb), and a surfactant (Hb). Before the step of transferring the print layer, the pretreatment liquid is applied to the surface to be transferred of the fabric.
After the step of transferring the printed layer, a step of applying a post-treatment liquid to the surface to be transferred of the fabric to which the printed layer is transferred and heating the printed layer is further provided.
The pretreatment liquid is water (A-c1); a combination of carboxylate anions and monovalent cations, and / or both of a cross-linking agent (G-c); urethane resin fine particles (F-c1); and surfactant. Contains the agent (H-c1),
The production method according to claim 1, wherein the post-treatment liquid contains water (A-c2), acrylic resin fine particles (F-c2), and a surfactant (H-c2). The production method according to any one of claims 1 to 7, wherein the base material contains a polyester-based film, a polyolefin-based film, or a polyurethane-based film. A decorative product including a cloth and a printing layer in contact with the cloth.
The printing layer is a water-based inkjet ink containing at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin fine particles (E). The ink contains 9 parts by mass of at least one substituted butanol selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol as the water-soluble organic solvent component (C). The resin fine particles (E) containing% or more and 27% by mass or less are fine particles of urethane resin having a glass transition temperature of 0 ° C. or less, and the content of the resin fine particles (E) in the ink is 2.5. It is formed by using a water-based inkjet ink having a mass% or more.
And the print layer is transferred onto the fabric.
Decorative items.