JP2002219863A - Transfer sheet for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet for ink jet recording, which has a high ink absorbency, a favorable color development and the image of which has metallic luster caused through the inlay of a metal and with which a highly decorative transferring image can be easily produced. SOLUTION: The transfer sheet for ink jet recording is produced by laminating a transferring layer and a support in the order named under the condition that the transferring layer includes a metallic powder or resin pieces deposited with a metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fabric, a film,
The present invention relates to a transfer sheet used when an image is formed on a transfer material such as a metal by transfer. More specifically, the present invention relates to a transfer sheet for ink jet recording in which an image is formed by an ink jet recording method.

[0002]

2. Description of the Related Art Ink-jet recording is a method in which minute droplets of ink are made to fly and adhere to a recording sheet such as paper by various operating principles to record images and characters. It has features such as easy multi-coloring, great flexibility in recording patterns, and no need for development-fixing, and is rapidly spreading in various applications as a recording device for various figures including Chinese characters and color images. Further, an image formed by the multi-color ink jet recording method can obtain an image comparable to multi-color printing by the plate making method. In addition, in applications requiring a small number of copies, it is being widely applied to the field of full-color image recording because of its low cost.

In recent years, there has been an increasing demand for performing color printing on various media using an ink jet printer capable of easily producing a full-color image. In particular, a printing technique using a transfer method has attracted attention because it can form an image even on a medium that is difficult to print directly with a printer.

Some transfer media using the ink jet recording method have been proposed so far. However, in the conventional transfer medium, the blank portion of the transfer layer to be transferred to the material to be transferred is solid, and no decorative material is provided by imparting metallic luster to the blank portion or scattering the blank portion. Such decoration can be applied before or after the transfer of the image-recorded transfer layer to the transfer material. For example, after decorating a metal film provided with a metal layer on the entire surface or a part of one side of the support on a material to be transferred, the image-recorded transfer layer is transferred onto the metal film to provide such decoration. Although it is possible to do so, there is a problem that the alignment of the transfer layer is difficult, the number of steps increases, and the operation becomes complicated.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a transfer sheet for ink jet recording which can easily transfer an image having a high decorative property to a material to be transferred such as a cloth, a film, or a metal. is there.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the composition of the transfer layer in order to solve the above problems, and as a result, have reached the following invention.

[0007] An invention of an ink-jet recording transfer sheet wherein a support and a transfer layer are sequentially laminated, wherein the transfer layer contains metal powder.

[0008] The present invention is directed to an ink-jet recording transfer sheet wherein a support and a transfer layer are sequentially laminated, wherein the transfer layer contains a resin piece on which a metal is deposited.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The transfer sheet for ink jet recording according to the present invention will be described in detail. The transfer sheet for ink jet recording of the present invention has a configuration in which a support and a transfer layer are sequentially laminated, and the transfer layer contains a metal powder or a resin piece on which metal is deposited. With this configuration, it is possible to obtain a transfer image excellent in decorativeness with a metallic luster scattered in the background by a simple operation.

As the metal powder according to the present invention, a metal powder having a metallic luster is preferably used. For example, aluminum, gold, silver, platinum, copper, zinc, tin, nickel and the like and alloys of these metals, for example, brass, stainless steel and the like can be mentioned. Further, those obtained by coloring these in various colors such as gold, red, blue and green by a vacuum deposition method or the like can also be used.

The particle size of the metal powder is determined in consideration of the visibility of the metal powder, the ink absorbency of the transfer layer, the adhesion of the transfer layer to the material to be transferred, the dispersibility of the metal powder in the transfer layer coating liquid, and the like. It is determined. The preferred range of the particle size is 0.1 μm or more and 1 mm or less, more preferably 1 μm or more and 500 μm or less, and even more preferably 5 μm or more and 300 μm or less. If the particle size is smaller than 0.1 μm, the metal powder is too fine and the visibility is likely to be poor. If it is larger than 1 mm, the ink absorbency of the transfer layer and the adhesiveness of the transfer layer to the transferred layer tend to be poor, and it is difficult to stably disperse the metal powder in the transfer layer coating liquid.

The object of the present invention can also be achieved by using a resin piece on which a metal usable in the above-mentioned metal powder is deposited instead of the metal powder used in the present invention. As a method for producing a metal-deposited resin piece, a method in which a metal is directly vapor-deposited on various organic pigments, a method in which a metal is vapor-deposited on one or both sides of a sheeted resin film, and then the resin film is strip-shaped, cubic, cylindrical Various methods such as the shape, a method of randomly cutting into small pieces, and a method of combining these are exemplified. When a metal powder is contained in the transfer layer, a transfer image having a uniform metallic luster can be obtained. On the other hand, when the transfer layer contains a resin piece in which metal is deposited, the shape of the metallic luster appears randomly due to the anisotropy of the shape of the resin piece, and a decorative effect different from the case where the metal powder is contained is obtained. can get.

Examples of the resin constituting the metal-deposited resin piece include polyethylene, polypropylene, polyisobutylene, polyethylene oxide, polyvinyl acetate, polyvinyl acetal, poly (meth) acrylic acid, poly (meth) acrylate, Heat of polyacrylic acid derivative, polyacrylamide, polyether, polyester, polycarbonate, cellulose resin, polyacrylonitrile, polyimide, polyamide, polyvinyl chloride, polyvinylidene chloride, polystyrene, thiochol, polysulfone, polyurethane, polybutadiene, etc. Thermosetting resin such as plastic resin, melamine resin, phenol resin, furan resin, xylene / formaldehyde resin, ketone / formaldehyde resin, urea resin, aniline resin, alkyd resin, epoxy resin RESIN, other copolymers of the monomers of these resins.

When the shape of the resin piece on which the metal is deposited is a true spherical shape, a cubic shape or a shape close to the shape, a particle size according to the particle size of the metal powder can be used. When the shape of the resin piece is a thin piece such as a strip, the length of the side having the maximum length is preferably 1 μm or more and 10 mm or less, more preferably 10 μm or more and 5 m or less.
m, more preferably 50 μm or more and 1 mm or less. If the maximum length is smaller than 1 μm, the resin piece on which the metal is deposited is too fine, and the visibility tends to be poor. If it is larger than 10 mm, the ink absorbency of the transfer layer and the adhesiveness of the transfer layer to the transfer receiving layer tend to be poor, and it is difficult to stably disperse the metal powder in the transfer layer coating liquid.

The transfer layer in the transfer sheet for ink jet recording of the present invention contains at least thermoplastic resin fine particles and a binder as components other than metal powder or metal-deposited resin pieces. Before the transfer image is formed, the thermoplastic resin fine particles according to the present invention are not formed into a film in the transfer layer and exist while maintaining the shape of the fine particles. For this reason, it becomes possible to absorb and hold the ink in the gap between the fine particles. When the transfer layer is heated and transferred to the material to be transferred, the fine particles are melted by heat. For example, when transferring to a cloth, these fine particles enter between the fibers and are fixed. It is possible to transfer the image to the transfer material.

The particle size of the fine particles of the thermoplastic resin is from 0.2 μm to 50 μm, preferably from 1 μm to 20 μm, more preferably from 3 μm to 15 μm from the viewpoints of ink absorption and image clarity. Particle size 0.2
If it is smaller than μm, the space between the thermoplastic resin fine particles becomes small, and it is difficult to obtain sufficient ink absorbency. Particle size 50
If it is larger than μm, the image resolution becomes low, and it is difficult to obtain a clear image.

It is preferable that the transfer sheet for ink jet recording of the present invention can easily form an image and transfer it to a material to be transferred at home or the like. That is, it is preferable that after the image is recorded on the transfer layer with a general-purpose ink jet printer, the transfer layer can be easily transferred to a cloth or the like with a household iron or the like. From this point, the minimum film forming temperature of the thermoplastic resin fine particles is preferably from 60 ° C to 200 ° C, more preferably from 70 ° C to 180 ° C, further preferably from 80 ° C to 180 ° C.
It is not less than 150 ° C and not less than 150 ° C. If the minimum film-forming temperature is lower than 60 ° C., the thermoplastic resin fine particles may be fused and formed into a film during storage, and the ink absorption originally possessed may be lost. In addition, since drying at the time of coating needs to be performed at a temperature equal to or lower than the minimum film forming temperature, manufacturing efficiency is reduced. If the minimum film forming temperature is higher than 200 ° C., high energy is required for transfer, and transfer to the transfer target material is difficult.

As the fine particles of the thermoplastic resin, any fine particles made of a water-insoluble thermoplastic resin can be used. For example, polyethylene, polypropylene, polyisobutylene, polyethylene oxide, polyvinyl acetate, polyvinyl acetal, poly (meth) acrylic acid, poly (meth) acrylate, polyacrylic acid derivatives, polyacrylamide, polyether, polyester, polycarbonate , Cellulosic resins, polyacrylonitrile, polyimide, polyamide, polyvinyl chloride, polyvinylidene chloride, polystyrene, thiochol, polysulfone, polyurethane, polybutadiene,
Other examples include copolymers of monomers of these resins.
Among them, polyethylene, polypropylene, poly (meth)
Acrylic acid, poly (meth) acrylate, polyvinyl acetate, polyvinyl chloride, polystyrene, polyurethane, polyamide, polybutadiene and copolymers thereof are preferably used.

The mixing ratio of the thermoplastic resin fine particles to the metal powder or the resin piece on which the metal is deposited is preferably 0.1 to 30 parts, more preferably 0.1 part to 100 parts of the thermoplastic resin fine particles. 5 to 20 parts, more preferably 1 to 15 parts. When the amount of resin powder on which metal powder or metal is deposited is less than 0.1 part, the obtained metallic luster is small, and when it is more than 30 parts, the ink absorptivity of the transfer layer and when the transfer layer is heated and transferred to the material to be transferred. Adhesion between the transfer layer and the material to be transferred is likely to be poor.

In the present invention, the binder used in the transfer layer is used for the purpose of fixing a substance such as thermoplastic resin fine particles, metal powder, or a metal-deposited resin piece in the transfer layer on the support. As the binder, for example, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate, oxidized starch, etherified starch, carboxymethylcellulose, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, soybean protein, silyl-modified polyvinyl alcohol, etc .; styrene-butadiene copolymer Coalescing,
Conjugated diene copolymer latex such as methyl methacrylate-butadiene copolymer; acrylic polymer such as acrylic acid and methacrylic acid ester polymer or copolymer, acrylic acid and methacrylic acid polymer or copolymer Latex; vinyl polymer latex such as ethylene-vinyl acetate copolymer; or functional group-modified polymer latex by monomer containing functional group such as carboxyl group of these various polymers; thermosetting of melamine resin, urea resin, etc. Aqueous adhesives such as synthetic resin adhesives; synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and alkyd resin;
Used in one or more types. Among these, a water-insoluble latex binder is preferred from the viewpoint of water resistance.

The glass transition temperature of the binder is such that thermoplastic resin fine particles, metal powder or a resin piece on which a metal is deposited are fixed to a support, and that the binder permeates and adheres to a material to be transferred such as a cloth during thermal transfer. And -50 ° C or higher and 50 ° C or higher in order to impart flexibility to the transfer layer transferred to the material to be transferred, and to have strength that can withstand washing and outdoor use.
The temperature is preferably not higher than -30 ° C and not higher than 40 ° C, more preferably not lower than -20 ° C and not higher than 30 ° C.

The ratio of the binder is preferably 1 part or more and 40 parts or less, more preferably 2 parts or more and 20 parts or less, further preferably 4 parts or more and 15 parts or less with respect to 100 parts of the thermoplastic resin fine particles. Binder ratio is 1
If the number is smaller than the number, the thermoplastic resin fine particles and the like cannot be sufficiently bonded, and a trouble such that the transfer layer is peeled off from the support during transportation of the printer is likely to occur. If the amount is more than 40 parts, the voids between the thermoplastic resin fine particles are filled with the binder, and the ink absorbency tends to be deteriorated.

The transfer layer of the present invention may contain a cationic resin. Secondary amine, 3
And quaternary ammonium salts. These cationic resins form insoluble salts with the sulfonic acid groups and carboxyl groups in the water-soluble direct dyes and water-soluble acid dyes that are the dye components of the aqueous ink. And the formation of an insoluble salt can suppress the flow or bleeding of the ink due to the dropping or moisture absorption of water, thereby improving the water resistance.

In the transfer layer of the present invention, a plasticizer is added for the purpose of imparting flexibility, transparency and adhesion to the transfer material to the transfer layer after the transfer to the transfer material. Can be. In particular, improving the flexibility of the transfer layer leads to an increase in the strength of the transfer layer, and the transfer layer is less likely to be torn even when it is exposed to wind and rain when washed or left outdoors.

In the present invention, the transfer layer further contains various organic and inorganic pigments, surfactants, hardeners, coloring dyes, coloring pigments, ultraviolet absorbers, antioxidants, pigment dispersants, defoamers, Leveling agent, preservative, optical brightener, viscosity stabilizer,
Various known additives such as a pH adjuster, a release agent, and a foaming agent can also be added. In addition, the transfer layer can be made of two or more different layers without any problem.
In this case, the metal powder or the resin piece on which the metal is deposited may be in any one of the plurality of transfer layers, and may be in all the transfer layers.

The coating amount of the transfer layer according to the present invention is preferably 15 g / m ² or more and 150 g / m ² or less, more preferably 30 g / m ² or more and 120 g / m ² or less, in terms of solid content. Preferably it is 40 g / m ² or more and 100 g / m ² or less. If the coating amount is less than 15 g / m ^2, it is difficult to obtain a good image because the ink absorbency of the transfer layer is insufficient, and the transferability of the transfer layer to the material to be transferred is deteriorated and a clear transfer image is obtained. It is hard to be. In addition, it becomes difficult to hold the metal powder or the resin piece on which the metal has been deposited in the transfer layer, so that the component tends to drop off. Coating amount is 150
If it exceeds g / m ² , the flexibility of the transfer layer tends to be lost.

As the support according to the present invention, any support can be used as long as it can be transported by a printer and has the necessary heat resistance to thermal transfer. For example,
Paper, nonwoven fabric, film and the like can be used. Specifically, papers such as high-quality paper, kraft paper, crepe paper, embossed paper, nonwoven fabrics, fabrics such as cotton cloth, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefin resins such as polyethylene and polypropylene, diacetate Examples include resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, resin films such as cellophane and celluloid, and supports obtained by coating (laminating) paper with a polyolefin resin such as polyethylene or polypropylene. Further, in order to improve the releasability of the transfer layer from the support to the material to be transferred, there is no problem in performing a surface release treatment on the support by a known method.

As an example of a method of performing a surface release treatment on a support, there is a method of providing a release layer on the support.
As a material for forming the release layer, as a heat-fusible material, for example, waxes such as carnauba wax, paraffin wax, microcrystalline wax, caster wax, stearic acid, palmitic acid, lauric acid, aluminum stearate, and stearic acid Higher fatty acids such as lead, barium stearate, zinc stearate, zinc palmitate, methylhydroxystearate, glycerol monohydroxystearate or derivatives thereof such as metal salts and esters, polyamide resins, petroleum resins, rosin derivatives, cumarone -Indene resins, terpene resins, novolak resins, styrene resins, olefin resins such as polyethylene, polypropylene, polybutene and oxidized polyolefin, and vinyl ether resins. In addition, a silicone resin, a fluorosilicone resin, a fluoroolefin vinyl ether terpolymer, a perfluoroepoxy resin, a thermosetting acrylic resin having a perfluoroalkyl group in a side chain, a vinylidene fluoride-based curable resin, and the like are also used. .

In order to produce the transfer sheet for ink jet recording of the present invention, it is necessary to provide a transfer layer on one surface of the support. The means include various blade coaters, roll coaters, air knife coaters, bar coaters, rod blade coaters, short dwell coaters, comma coaters, die coaters, reverse roll coaters, kiss coaters, curtain coaters, extrusion coaters, gate roll coaters, A coating device such as a gravure coater or a microgravure coater can be used.

The transfer sheet for ink jet recording of the present invention forms an image on the transfer layer by using a commercially available general-purpose printer, transfers the image on the transfer layer to the transfer target by means such as heating, and transfers the image to the transfer target. Used to form an image.
The color material to be used is not particularly limited, and conventionally known dye inks and pigment inks can be used.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples.

Preparation of Transfer Layer Coating Liquid 1 Ethylene-vinyl acetate emulsion (Chemipearl V-200; manufactured by Mitsui Chemicals) 100 as thermoplastic resin fine particles
Part, aluminum powder (particle diameter 100 μm) 1 as metal powder
0 parts, styrene-acrylic emulsion (GD41; manufactured by NSC) 10 parts as a binder, and polyamide-epichlorohydrin resin (W
S547; manufactured by Nippon PMC Co., Ltd.) (10 parts), and the mixture was adjusted to a solid concentration of 35%.

Preparation of Transfer Layer Coating Solution 2 Aluminum was deposited on both sides of a 50 μm thick PET film. This PET film was cut into a square of 200 μm × 2 mm to produce a resin piece on which metal was deposited. 10 parts of a resin piece obtained by vapor deposition of the metal thus obtained, 100 parts of an ethylene-vinyl acetate emulsion (Chemipearl V-200; manufactured by Mitsui Chemicals) as thermoplastic resin fine particles, and a styrene-acrylic emulsion (GD41;
Nippon NSC) 10 parts, polyamide epichlorohydrin resin (WS547; Japan P
MC) (10 parts), and the mixture was prepared.
%.

Preparation of transfer layer coating liquid 3 Ethylene-vinyl acetate emulsion (Chemipearl V-200; manufactured by Mitsui Chemicals) 100 as fine particles of thermoplastic resin
Part, aluminum powder (particle diameter 100 μm) 1 as metal powder
0 parts, styrene-acrylic emulsion (GD41; manufactured by NSC) 10 parts as a binder,
This was adjusted to a solid concentration of 35%.

Preparation of Transfer Layer Coating Solution 4 Ethylene-vinyl acetate emulsion (Chemipearl V-200; manufactured by Mitsui Chemicals) 100 as thermoplastic resin particles
Parts, styrene-acrylic emulsion (GD41; manufactured by NSC) 10 parts as a binder, and polyamide / epichlorohydrin resin (WS) as a cationic resin
547; manufactured by Nippon PMC Co., Ltd.).
The solid content concentration was 35%.

Example 1 A commercially available release paper was used as a support, and the coating amount obtained in Preparation 1 of the transfer layer coating liquid was applied to a release-treated surface of the release paper after drying using a comma coater. Was adjusted to 70 g / m ² and dried by hot air at 60 ° C. to obtain a transfer sheet for inkjet recording of the present invention.

Example 2 A commercially available release paper was used as a support, and the coating liquid obtained in Preparation 2 of the transfer layer coating liquid was dried on a release-treated surface of the release paper using a comma coater. Was adjusted to 70 g / m ² and dried by hot air at 60 ° C. to obtain a transfer sheet for inkjet recording of the present invention.

Example 3 A commercially available release paper was used as a support, and the coating amount obtained in Preparation 4 of the transfer layer coating liquid was dried on a release-treated surface of the release paper using a comma coater. Was adjusted to 15 g / m ² and dried by hot air at 60 ° C. The coating liquid obtained in Preparation 3 of the transfer layer coating liquid was further dried on the transfer layer coating surface of the sheet thus obtained using a comma coater so that the coating amount after drying was 60 g /.
m ² and dried by hot air at 60 ° C. to obtain a transfer sheet for ink jet recording of the present invention.

Example 4 A commercially available release paper was used as a support, and the coating liquid obtained in Preparation 3 of the transfer layer coating liquid was dried on a release-treated surface of the release paper using a comma coater. Was adjusted to 60 g / m ² and dried with hot air at 60 ° C. Using a comma coater, the applied amount of the coating solution obtained in 4 obtained in the preparation of the coating solution for the transfer layer was further applied to the coated surface of the transfer layer of the sheet thus obtained by coating with a comma.
The coating was applied at 5 g / m ² and dried by hot air at 60 ° C. to obtain a transfer sheet for inkjet recording of the present invention.

Comparative Example 1 A commercially available release paper was used as a support, and the coating amount obtained in Preparation 4 of the transfer layer coating liquid was dried on a release-treated surface of the release paper using a comma coater. Was applied at 25 g / m ² and dried by hot air at 60 ° C. to obtain a transfer sheet for inkjet recording.

[Evaluation] 1) Ink Absorbability After cutting the transfer sheets prepared in Examples and Comparative Examples to A4 size, black and cyan were applied to the transfer layer side of the transfer sheet by an ink jet printer (PM-750C manufactured by Seiko Epson). , Magenta and yellow 100%, and blue (mixed color of cyan and magenta), green (mixed color of cyan and yellow), and 200% of each color of red (mixed color of magenta and yellow). The ink absorbency of each transfer sheet was determined based on the following criteria. A: No bleeding of the ink was observed in each color, and the ink absorption was good. ：: In the solid printing portion of 200%, although ink bleeding is slightly observed depending on the color, it is at an acceptable level. 100
%, The ink absorbency of the solid printed portion is good. ×: Clear ink bleeding is seen in the 200% solid printing portion. Even in the 100% solid printing portion, ink bleeding is observed depending on the color, and the ink absorbency is poor.

2) Print Density The transfer sheets prepared in Examples and Comparative Examples were cut to A4 size, and black, cyan, magenta, and yellow were applied to the transfer layer side of the transfer sheet with an ink jet printer (PM-750C manufactured by Seiko Epson). The solid printing of 100% for each color was performed. After printing, the transfer layer side of the transfer sheet was brought into close contact with a 100% cotton white T-shirt, and an iron heated to about 200 ° C. was contacted from the support side of the transfer sheet to perform transfer. After the transfer sheet was sufficiently cooled, the support was peeled off to obtain a transfer image. The print density of each color of the transfer image thus obtained was measured using Macbeth RD919. Larger values indicate higher print density and better printability.

3) Decoration The transfer sheets prepared in Examples and Comparative Examples were cut to A4 size, and an illustration image was printed on the transfer layer side of the transfer sheet using an ink jet printer (PM-750C manufactured by Seiko Epson). . After printing, the transfer layer side of the transfer sheet is brought into close contact with a 100% cotton white T-shirt,
The transfer was performed by bringing the heated iron into contact with the transfer sheet from the support side. After the transfer sheet was sufficiently cooled, the support was peeled off to obtain a transfer image. The decorativeness of the transfer image thus obtained was determined according to the following criteria. ：: The image has a glittering metallic luster and is highly decorative. X: The image has no metallic luster at all.

[0044]

[Table 1]

As is clear from Table 1, the transfer sheet for ink jet recording of the present invention in which the transfer layer contains a metal powder or a resin piece on which a metal is vapor-deposited imparts a metallic luster to the image as if the metal were scattered. It is possible to easily produce a transfer image with high decorativeness.
Even if the transfer layer containing the metal powder or the resin piece on which the metal is vapor-deposited is a single layer as in Examples 1 and 2,
The same effect can be obtained by a configuration in which the transfer layer has a two-layer structure as described above and at least one layer contains a resin piece obtained by depositing metal powder or metal.

[0046]

The transfer sheet for ink jet recording according to the present invention is characterized in that the transfer layer contains a metal powder or a resin piece on which metal is deposited. With this configuration,
It is possible to impart metallic luster to the image as if metal were scattered, and it is possible to easily produce a transferred image with high decorativeness.

Claims (2)

[Claims] 1. An ink-jet recording transfer sheet comprising a support and a transfer layer sequentially laminated, wherein the transfer layer contains metal powder. 2. A transfer sheet for ink jet recording, in which a support and a transfer layer are sequentially laminated, wherein the transfer layer contains a resin piece on which a metal is deposited.