WO2021240726A1

WO2021240726A1 - Aqueous inkjet ink, transfer film, printed matter, and production method thereof

Info

Publication number: WO2021240726A1
Application number: PCT/JP2020/021129
Authority: WO
Inventors: 新二田渕
Original assignee: ローランドディー．ジー．株式会社
Priority date: 2020-05-28
Filing date: 2020-05-28
Publication date: 2021-12-02
Also published as: JPWO2021240726A1; JP7495495B2

Abstract

Provided is aqueous inkjet ink that can form a printed layer for a transfer film, the aqueous inkjet ink excelling in printing quality, transfer quality, and bending resistance, and being capable of adhering directly to leather. The aqueous inkjet ink contains at least water (A), a pigment (B), a water-soluble organic solvent component (C), a silicone-based surfactant (D), and resin microparticles (E). The ink contains, as the water-soluble organic solvent component (C), 9-27 mass% of at least one substituted butanol selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol. The resin microparticles (E) are microparticles of a urethane resin having a glass transition temperature of 0℃ or less. The content of the resin microparticles (E) in the ink is 2.5 mass% or more. The aqueous inkjet ink is used for forming a printed layer for a transfer film.

Description

Water-based inkjet ink, transfer film, printed matter and its manufacturing method

The present invention relates to a water-based inkjet ink for forming a print layer of a transfer film. The present invention also relates to a transfer film. The present invention also relates to a printed matter and a method for producing the same.

Conventionally, in order to decorate leather such as natural leather, synthetic leather, artificial leather, and recycled leather, characters, images, etc. have been printed on the leather surface. In such printing, since the printing target is leather, not only the print quality but also the bending resistance of the printed layer and the adhesiveness of the printed layer to the leather are required, and the texture of the leather is further affected by the printed layer. It is required not to be damaged. As one of the printing methods on leather, a transfer printing method using a transfer film is known. In the transfer printing method, transfer quality is also required.

In one of the conventional transfer printing methods for leather, printing is performed on the entire surface of the leather using a transfer film including at least a printing layer, an adhesive layer, and a polyurethane layer (for example, Patent Documents 1 to 3). reference). On the other hand, in recent years, there has been an increasing demand for a printing method capable of decorating a part of the leather surface on demand, and as a transfer film capable of printing on a part of the leather surface on demand, a printing layer and an adhesive layer are used. A transfer film in which each layer is formed by an inkjet method has been developed (see, for example, Patent Documents 4 and 5).

Japanese Unexamined Patent Publication No. 2007-111867 Japanese Unexamined Patent Publication No. 2007-100209 Japanese Patent No. 3069064 Japanese Unexamined Patent Publication No. 6074563 Japanese Unexamined Patent Publication No. 2013-141787

However, in the transfer printing method of the prior art, the print layer cannot be directly adhered to the leather, and the print layer is adhered to the leather via the adhesive layer. Therefore, there is a problem that the texture of the leather may be impaired by this adhesive layer. Further, providing the adhesive layer on the transfer film requires a step of forming the adhesive layer, which causes a decrease in the productivity of the transfer film.

The present invention has been made in view of the above points, and the present invention can form a printed layer of a transfer film which is excellent in print quality, transfer quality, and bending resistance and can be directly adhered to leather. It is an object of the present invention to provide a water-based inkjet ink.

The water-based inkjet ink according to the present invention contains 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. The water-based inkjet ink according to the present invention is for forming a print layer of a transfer film.

From another aspect, the transfer film according to the present invention has a printing layer formed by the above-mentioned water-based inkjet ink and a film base material.

From another aspect, the printed matter according to the present invention comprises a printed matter formed by the water-based inkjet ink and a transferred matter in contact with the printed layer, and the printed matter in contact with the printed layer. The relative permittivity of the surface is 2.8 or more and 5.5 or less.

From another aspect, the method for producing a printed matter according to the present invention includes a step of preparing the transfer film, a step of arranging the printed layer of the transfer film so as to be in contact with the transferred object, and a step of arranging the transfer film. The present invention comprises a step of lowering the pressure on the printed layer side to be lower than the pressure on the film substrate side of the transfer film so that the printed layer of the transfer film is brought into close contact with the transferred matter.

According to the present invention, there is provided a water-based inkjet ink that is excellent in print quality, transfer quality, and bending resistance, and can form a print layer of a transfer film that can be directly adhered to leather.

[Water (A)]
The water-based inkjet ink according to the present invention 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 from the viewpoint of preventing contamination with impurities, ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water is preferable, and ion-exchanged water is preferable. 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, and even 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, precipitating 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 cyanide pigments 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 Orange 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, and the image quality 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 high, cracks occur in the print layer, and the image quality 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. 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. The content of glycol monoethers 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 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, still more preferably 20% 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.

[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, still more preferably 2.5% by mass or less.

[Resin fine particles (E)]
In the present invention, as the resin fine particles (E), urethane resin fine particles having a glass transition temperature (Tg) of 0 ° C. or lower are used. Since the water-based inkjet ink contains fine particles of urethane resin having a glass transition temperature of 0 ° C. or lower, a print layer having excellent transfer quality can be formed on the film substrate, and the print layer can be formed on the film substrate. In addition to bending resistance, it has excellent adhesion to transferred materials (particularly leather). Therefore, the printed layer can be directly adhered to the leather.

The glass transition temperature of the urethane resin is preferably −5 ° C. or lower, more preferably −10 ° C. or lower, and further 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 transfer quality improving effect, the bending resistance improving effect, and the adhesiveness improving effect to the transferred body (particularly leather) 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 when the mass ratio becomes large, the transfer quality improving effect and the bending resistance improving effect, In addition, the effect of improving the adhesiveness to the transferred material (particularly leather) tends to be small. 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.

The water-based inkjet ink according to the present invention is for forming a print layer of a transfer film. A transfer film can be produced by forming a printing layer on a film substrate by an inkjet method using the water-based inkjet ink according to the present invention while suppressing the occurrence of image bleeding and cracking of an image. That is, according to the water-based inkjet ink according to the present invention, a printed layer can be formed on a film substrate with excellent print quality. The printed layer formed on the film substrate can be transferred directly to a transfer target such as leather without using an adhesive layer, and is excellent in transfer quality at this time. Further, since it is not necessary to provide an adhesive layer on the transfer film, according to the water-based inkjet ink according to the present invention, the transfer film can be produced only by forming a print layer on the film substrate. Therefore, according to the water-based inkjet ink according to the present invention, the productivity of the transfer film is also excellent. In addition, since the print layer of the transfer film is formed by an inkjet method, the manufactured transfer film is very suitable for decorating a part of the leather surface on demand, and decorates the entire surface of the leather. It can also be used for. Further, the printed layer transferred from the transfer film to the transferred body has excellent bending resistance and also has excellent adhesiveness to the transferred body (particularly leather).

Therefore, from another point of view, the present invention is a transfer film having a printing layer formed by the above-mentioned water-based inkjet ink and a film substrate.

As the film base material, a known transfer film base material used in a transfer printing method such as leather 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. Among them, a polyester-based film is preferable, and a polyethylene terephthalate film is more preferable, because the transfer quality is excellent. Therefore, the film base material of the transfer film according to the present invention preferably contains a polyester-based film. Further, as the base film, a stretchable film (particularly, a polyolefin-based film, a polyurethane-based film, etc.) can also be preferably used. 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 base material 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.

The transfer film has a print layer formed by the above-mentioned water-based inkjet ink. Therefore, the print layer is a layer of the dried product of the above-mentioned water-based inkjet ink. The print layer is in contact with the transfer film.

The adhesive layer is not essential in the transfer film according to the present invention. Therefore, the transfer film according to the present invention typically includes only a film substrate and a printing layer. However, the transfer film according to the present invention may further have a release liner or the like for the purpose of protecting the print layer.

The transfer film according to the present invention is produced by ejecting the above-mentioned water-based inkjet ink onto the above-mentioned film substrate by an inkjet method and drying the ejected water-based inkjet ink using a known inkjet recording device. be able to.

A suitable example of a method for producing a transfer film will be described. Examples of the suitable manufacturing method include a step of preheating the film substrate (preheating step), a step of ejecting the above-mentioned aqueous inkjet ink onto the preheated film substrate (ejection step), and an ejected aqueous solution. A step of drying the inkjet ink to form a print layer (drying step) is provided.

The preheating step can be performed, for example, by heating the film substrate with the preheater using an inkjet recording device equipped with a preheater. Alternatively, this can be done 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 40 ° C. or higher and 50 ° C. or lower. By performing the preheating step, the quality of the image formed on the film substrate can be further improved.

The ejection step can be performed by ejecting 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.

The drying step 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.

The transfer film according to the present invention can be used for decoration by the transfer method according to a known method. In particular, according to the transfer film according to the present invention, the printed layer of the transfer film can be directly transferred to leather such as natural leather, synthetic leather, artificial leather, and recycled leather without using an adhesive layer. When the transfer is performed, the transfer quality, the bending resistance of the transferred print layer, and the adhesiveness to the leather are excellent. Therefore, the transfer film of the present invention is suitable for leather printing. Further, the transfer film according to the present invention can decorate an article having a surface relative permittivity of 2.8 or more and 5.5 or less, including leather, with excellent transfer quality.

Therefore, from another viewpoint, the present invention comprises a printed matter formed by the above-mentioned water-based inkjet ink and a transferred matter that comes into contact with the printed layer, and the surface of the transferred matter that comes into contact with the printed layer. It is a printed matter having a relative permittivity of 8 or more and 5.5 or less.

Examples of the material of the transferred body having a surface relative permittivity of 2.8 or more and 5.5 or less include urethane resin, vinyl chloride resin, acrylic resin, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate, and natural materials. Examples include leather. Here, urethane resin, vinyl chloride resin, and acrylic resin are used for synthetic leather / artificial leather applications. Therefore, the transferred body is preferably made of urethane resin, vinyl chloride resin, acrylic resin, or natural leather. Alternatively, the transferred body is preferably made of natural leather, synthetic leather, or artificial leather. The relative permittivity of the surface of the transferred body can be measured, for example, in accordance with the transformer bridge method of ASTM D150 under the condition of a measurement frequency of 1 MHz.

Further, it is sufficient for the transferred body to have at least the surface on which the print layer is transferred 2.8 or more and 5.5 or less. Therefore, in one embodiment of the present invention, the transferred body has a coating having a relative permittivity of 2.8 or more and 5.5 or less. The transfer material may have a coating at least on the portion where the print layer is transferred. With such a coating, even articles having a relative permittivity outside the range of 2.8 or more and 5.5 or less can be decorated with the above transfer film.

The material of the coating is not particularly limited as long as the relative permittivity is 2.8 or more and 5.5 or less. It is preferably a coating of at least one resin selected from the group consisting of vinyl chloride resin, urethane resin, and acrylic resin.

In the printed matter according to the present invention, the transferred body and the printed layer are in direct contact with each other. That is, in the printed matter according to the present invention, the transferred body and the printed layer are in contact with each other without interposing the adhesive layer. Therefore, the printed matter according to the present invention usually has a printed layer as a single layer on the surface of the transfer target. Therefore, there is an advantage that the texture of the transferred body is not impaired. In addition, the print layer has high bending resistance. In addition, the transferred print layer is particularly adhesive to leather. Therefore, in the printed matter according to the present invention, it is advantageous that the transferred body is made of leather.

The printed matter according to the present invention can be produced by using the above-mentioned transfer film. For example, it can be produced as follows. First, the transfer film is placed on a surface having a relative permittivity of 2.8 or more and 5.5 or less of the printed matter, and the printed matter is pressed while heating to transfer the printed layer of the transfer film to the transferred body. If necessary, the transferred print layer is heated and pressurized to fix the printed layer.

The above method is particularly suitable when the surface of the transferred body is flat. On the other hand, when the transferred body is a three-dimensional object, the following method is suitable. In the present specification, "the transferred object is a three-dimensional object" means that when the surface of the printed layer of the transfer film is a flat surface, at least a part of the surface of the transferred object to which the print layer is transferred is defined. Refers to the case where the surface of the print layer is inclined with respect to the surface of the print layer or has a curved surface. The three-dimensional object typically includes an article having a curved surface, a convex portion, a concave portion, an inclined surface, or the like in part.

Suitable methods include the step of preparing the transfer film, the step of arranging the print layer of the transfer film so as to be in contact with the transferred object, and the pressure on the print layer side of the transfer film. A method for producing a printed matter, comprising a step of bringing the printed layer of the transfer film into close contact with the transferred object by lowering the pressure on the film substrate side of the transfer film. Therefore, from another aspect, the method for producing a printed matter according to the present invention is this method for producing a printed matter.

The step of preparing the transfer film can be performed, for example, by implementing a suitable specific example of the above-mentioned method for producing a transfer film. Further, another person may manufacture the above-mentioned transfer film and prepare it by purchasing the transfer film or the like.

In the process of bringing the transferred body into close contact, the printed layer of the transfer film is brought into close contact with the transferred body by utilizing the pressure difference. Examples of the method for causing the pressure difference include a method of reducing the pressure on the print layer side of the transfer film to less than 1 atm and a method of pressurizing the pressure on the film substrate side to more than 1 atm. Since it is easy to carry out, a method of reducing the pressure on the printing layer side of the transfer film to less than 1 atm is preferable. The adhesion step is preferably performed by heating the transfer film. The heating temperature may be appropriately determined depending on the film substrate of the transfer film and the constituent materials of the transferred body, and is, for example, 110 ° C. or higher and 160 ° C. or lower.

The step of bringing the transferred body into close contact can be performed, for example, by using a known vacuum forming machine that forms the decorative film in close contact with the surface of the adherend. Specifically, for example, the vacuum forming machine includes a closed chamber that can be opened and closed in the vertical direction, a table provided at the lower part of the chamber, and a heater. After placing the transfer target on the table of the vacuum forming machine, the lower chamber and the upper chamber are closed while sandwiching the transfer film. As a result, a closed space surrounded by the lower part of the chamber and the transfer sheet and a closed space surrounded by the upper part of the chamber and the transfer sheet are formed. Then, the transfer sheet is heated by the heater. When the pressure on the print layer side of the transfer film is reduced to less than 1 atm, the pressure in the closed space surrounded by the lower part of the chamber and the transfer sheet is reduced. On the other hand, when the pressure on the film substrate side is pressurized to exceed 1 atm, the closed space surrounded by the upper part of the chamber and the transfer sheet is pressurized. The printed layer of the transfer film is brought into close contact with the transferred object by utilizing the pressure difference between the closed space surrounded by the upper part of the chamber and the transfer sheet and the closed space surrounded by the lower part of the chamber and the transfer sheet. Thereby, the adhesive layer of the transfer sheet can be transferred to the transferred body.

Here, it is preferable that the film base material is expandable, and at this time, it is preferable that the film base material contains a polyolefin-based film or a polyurethane-based film. When the film substrate is stretchable, the print layer of the transfer film and the transfer target can be more easily adhered to each other. In addition, in this specification, "stretchable" means that the tensile elongation measured according to ASTM D882 at the transfer temperature is 150% or more. The tensile elongation is preferably 200% or more, more preferably 300% or more, and further preferably 500% or more.

In order to transfer more reliably, after the adhesion step, a step of further reducing the pressure or pressurizing and heating to fix the printed layer to the transferred object may be performed. The heating temperature at this time may be appropriately determined according to the material of the transferred body, and is, for example, 110 ° C. or higher and 160 ° C. or lower.

After that, by peeling the film base material of the transfer film from the transferred object, a printed matter including the transferred printed layer can be obtained.

According to this printed matter manufacturing method, it is possible to decorate a three-dimensional object having irregularities or curved surfaces on the surface to be decorated with a single transfer. This method for producing a printed matter is very advantageous when the transferred object is a three-dimensional object, but the transferred object does not have to be a three-dimensional object. Therefore, according to this method for manufacturing a printed matter, there are few restrictions on the shape of the transferred body and the decorative position, and printing can be easily performed using the transfer film. In particular, according to this printed matter manufacturing method, printing by the transfer method is possible with a small number of steps, including the preparation of a transfer film.

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

<Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-4>
[Preparation of transfer film]
Each component shown in Tables 1 to 4 was uniformly mixed in the mass ratio shown in each table to obtain an inkjet ink set of each Example and each Comparative Example. Each inkjet ink set is composed of cyan (C), magenta (M), yellow (Y), black (K), and white (Wh) ink. This inkjet ink set is Roland Dee. 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 release transfer polyester film "Panapeel TP-3" manufactured by Panac (this process is called a "printing process"). The printed polyester film was dried on a hot plate set at 100 ° C. for 30 minutes to obtain a transfer film having a printing layer on the polyester film.

[Printing by transfer method]
The transfer film and the artificial leather were superposed so that the printed layer of the obtained transfer film came into contact with the artificial leather "Cordre" manufactured by Teijin Limited. This was pressed at 120 ° C. for 1 minute with an iron to transfer the printed layer to artificial leather (this step is referred to as a "transfer step"). Further, the silicon paper was placed on the transferred printing layer and pressed at 120 ° C. for 1 minute with an iron to fix the printing layer on the artificial leather. In this way, an artificial leather to which the printing layer was transferred was obtained.

For each of the above Examples and Comparative Examples, the image quality, transfer quality, bending resistance, and adhesiveness were evaluated by the following methods.

[Image quality]
The image printed on the transfer film in the printing process was a full solid image having 7 pt white characters. The image quality of the printed layer of the obtained transfer film was evaluated according to the following criteria. The results are shown in the table.
A: No blurring or cracking in the image B: Blurring or cracking in a part of the image C: Blurring or cracking in the entire image

[Transfer quality]
In the transfer step, the state in which the printed layer was transferred from the polyester film to the artificial leather was observed, and the transfer quality was evaluated according to the following criteria. The results are shown in the table.
A: The entire print layer is transferred from the polyester film to the artificial leather B: The transferred print layer is partially chipped C: The transferred print layer is notably chipped, or the print layer is not transferred. Or the transferred print layer spoils the texture of the artificial leather

[Bending resistance]
The artificial leather to which the printed layer was transferred was bent 10,000 times by a bending resistance test method according to JIS K6550: 1994, and the bending resistance was evaluated according to the following criteria. The results are shown in the table.
A: The transferred print layer is not cracked B: A part of the transferred print layer is cracked C: The entire transferred print layer is cracked

[Adhesion evaluation]
Nichiban's cellophane tape was attached to the printed layer transferred to the artificial leather, and then the cellophane tape was peeled off. The condition at that time was evaluated according to the following criteria. The results are shown in the table.
A: The transferred print layer is not peeled off from the artificial leather at all B: A small part of the surface of the transferred print layer adheres to cellophane tape (registered trademark), but the print layer itself is not peeled off from the artificial leather C : A part of the transferred print layer is peeled off from the artificial leather, and the base of the artificial leather is exposed.

(The numerical value for each component in each 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)
Superflex 470 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Aqueous emulsion of urethane resin (resin Tg: -31 ° C, solid content 38% by mass)
Viniblanc 700 (manufactured by Nissin Chemical Industry Co., Ltd.): Aqueous emulsion of core-shell particles of polyvinyl chloride-acrylic resin (resin Tg: 70 ° C, solid content 30% by mass)

As shown in Tables 1 to 4, by using the water-based inkjet ink sets of Examples 1-1 to 1-8 within the scope of the present invention, bending resistance and leather while suppressing image bleeding and cracking. It was possible to form a print layer having excellent adhesiveness to the ink.

<Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-2>
Using the transfer film prepared using the water-based inkjet ink set of Example 1-1, the materials shown in Table 5 were printed by the transfer method by the same method as described above. The results are shown in the table.

As shown in Table 5, the transfer film produced by using the water-based inkjet ink set of Example 1-1 within the scope of the present invention has a relative permittivity of 2.8 or more and 5.5 on the surface of the transferred body. It can be seen that transfer is possible when the following is true.

<Example 3-1>
A transfer material having an acrylic resin coating layer was prepared by applying an acrylic resin paint (a metal undercoat spray manufactured by Nippe Home Products) to a metal toy car and drying it. The transferred material was placed on the table of a vacuum forming machine. A transfer film prepared using the water-based inkjet ink set of Example 1-1 was attached to a vacuum forming machine and heated to 130 ° C. The chamber of the vacuum forming machine was closed, the pressure on the transferred body side was reduced, and the transferred body and the transfer film were bonded together. Then, the pressure was reduced and the heat was applied to fix the printed layer of the transfer film on the transfer target.

When the transferred body to which the transfer film was attached was taken out from the vacuum forming machine and the transfer film was peeled off, only the printed layer was transferred to the transferred body.

The present invention is very useful for decorating articles having a surface relative permittivity of 2.8 or more and 5.5 or less, including leather.

Claims

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.
For forming a print layer of a transfer film,
Water-based inkjet ink.
The water-based inkjet ink according to claim 1, which contains the substituted butanol in an amount of 12% by mass or more and 20% by mass or less.
The water-based inkjet ink according to claim 1 or 2, wherein the content of the resin fine particles in the ink is 3.0% by mass or more and 15% by mass or less.
The print layer formed by the water-based inkjet ink according to any one of claims 1 to 3 and
A transfer film having a film substrate.
The transfer film according to claim 4, wherein the film base material contains a polyester-based film, a polyolefin-based film, or a polyurethane-based film.
The print layer formed by the water-based inkjet ink according to any one of claims 1 to 3 and
A transfer material that comes into contact with the print layer is provided.
A printed matter having a relative permittivity of 2.8 or more and 5.5 or less on the surface of the transferred body in contact with the printed layer.
The printed matter according to claim 6, wherein the transferred body is made of urethane resin, vinyl chloride resin, acrylic resin, or natural leather.
The printed matter according to claim 6, wherein the surface of the transferred body has a coating having a relative permittivity of 2.8 or more and 5.5 or less.
The printed matter according to claim 8, wherein the coating is a coating of at least one resin selected from the group consisting of a vinyl chloride resin, a urethane resin, and an acrylic resin.
The step of preparing the transfer film according to claim 4 or 5, and
A step of arranging the print layer of the transfer film so as to be in contact with the transfer target,
A step of lowering the pressure on the print layer side of the transfer film to be lower than the pressure on the film substrate side of the transfer film so that the print layer of the transfer film is brought into close contact with the transfer target.
A method for manufacturing printed matter.
According to claim 10, in the step of bringing the transferred body into close contact, the pressure on the print layer side of the transfer film is reduced to less than 1 atm, or the pressure on the film substrate side of the transfer film is pressed to exceed 1 atm. The manufacturing method described.
The manufacturing method according to claim 10 or 11, wherein the transferred object is a three-dimensional object.
The production method according to any one of claims 10 to 12, wherein the film base material contains a polyolefin-based film or a polyurethane-based film and is expandable.