JPH0911699A - Iris transfer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an iris transfer material capable of seeing through a grace, beautiful, clear iris having high brightness and also having good fastness such as wear resistance, anti-abrasion, chemical resistance, solvent resistance and the like by providing an evaporated thin film structural body consisting of a combination of evaporated thin films of a specific metal or metallic compound. SOLUTION: The base material 1 has a mold release agent layer 2, a first protection layer or a coloring layer 3, a pictorial pattern layer 4, a second protection layer or coloring layer 5 laminated thereon. Also, an evaporated thin film structural body 6 is formed thereon. The evaporation thin film structural body 6 is of a laminate of a low reflecting metal or metallic compound evaporated thin film 7 having a reflection coefficient of 15-35% selected from chrome, titanium, zinc, cupric oxide, chromium oxide, and zinc oxide, a low refraction metallic oxide or metallic fluoride evaporated thin film 8 having a refraction coefficient of 0.5-2.5 selected from silicon monoxide, silicon dioxide, and the like, and a high reflecting evaporated thin film 9 having a reflection coefficient of 75-98% selected from aluminum, tin, and the like. Thus, an iris can be obtained having two colors.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iris transfer material having high glitter.

[0002]

2. Description of the Related Art Conventionally, iris foil has been widely used for traditional crafts such as cloth, gold thread, silver thread, and drawing foil. Such an iris foil is conventionally manufactured by coating a solution of a synthetic resin on a suitable base material with a roll coater, drying it, and laminating it on a thin film that causes optical interference. Therefore, according to such an iris foil, uneven dot and uneven application of the solution occur during its production, and a beautiful iris cannot be obtained. Furthermore, in terms of physical properties, solvent resistance and chemical resistance are also high. , Light resistance, weather resistance, abrasion resistance, scratch resistance, etc. are poor, and the iris effect is reduced in a short period of time.

On the other hand, there is also known an iris foil formed by sublimation vapor deposition of zinc sulfide, antimony oxide, bismuth, cadmium sulfide, etc. on a substrate, but these have poor iris effect and fastness such as weather resistance. In addition, it is scarce and the material is toxic, so there is a problem in practical use.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in conventional iris foils, and is a vapor deposition comprising a combination of vapor deposition thin films of a novel metal or metal compound. By having a thin film structure, an iris with grace, beauty, vividness and high brightness can be seen through, and further wear resistance, scratch resistance, chemical resistance, solvent resistance,
It is an object of the present invention to provide an iris transfer material having excellent fastness such as weather resistance.

[0005]

A highly bright iris transfer material according to the present invention has a release agent layer on a base material, and a transparent or semitransparent protective layer or a coloring layer on the release agent layer. Chrome on top,
A low-reflectivity metal or metal compound vapor-deposited thin film having a reflectance of 15 to 35% selected from titanium, zinc, cupric oxide, chromium oxide, and zinc oxide, silicon monoxide, silicon dioxide, indium oxide, indium tin oxide, and oxidation. Refractive index selected from titanium, magnesium fluoride and calcium fluoride
0.5-2.5 low-refractive-index metal oxide or metal fluoride vapor-deposited thin film and high-reflectivity metal vapor-deposited thin film having a reflectance of 75-98% selected from aluminum, tin, nickel, silver and alloys thereof. And a transparent or semi-transparent protective layer or a coloring layer and a heat-sensitive adhesive layer in this order. .

The transfer material according to the present invention will be described below with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a main part showing a transfer material as a preferred embodiment according to the present invention. In this transfer material, the release agent layer 2 is formed on the base material 1,
A first protective layer or colored layer 3 made of a transparent or translucent resin, a transparent or translucent picture pattern layer 4 and a second protective layer made of a transparent or translucent resin on the release agent layer 2. Alternatively, the colored layer 5 is laminated in this order. Further, a vapor deposition thin film structure 6 made of a combination of metal vapor deposition thin films of metals or metal compounds is formed on the second protective layer or colored layer 5. According to the present invention, this vapor deposition thin film structure 6 is formed by laminating a low reflective vapor deposition thin film 7, a low refractive vapor deposition thin film 8 and a high reflective vapor deposition thin film 9 in this order.
Furthermore, a third protective layer or colored layer 10 made of a transparent or semitransparent resin and a heat-sensitive adhesive layer 11 are formed on the highly reflective vapor deposited thin film 9 of the vapor deposited thin film structure 6.

In the present invention, the substrate is usually a transparent or translucent film made of synthetic resin, and examples of the synthetic resin include polyethylene terephthalate, polyester, polyimide, polyphenylene sulfide and polyethylene. Phthalates, polyamides, polycarbonates, polypropylenes, polyethylenes, polyvinyl chlorides, polystyrenes, polyvinylidene chlorides, etc. are used. Cellophane is also used. These are used alone or in a plurality of layers.

A release agent layer is formed on such a substrate. The release agent layer is not particularly limited,
For example, in addition to resins such as silicone resin and fluorine resin, waxes such as polyethylene wax, carnauba wax, paraffin wax, and beeswax, fatty acid esters and various surfactants are used. These are used alone or in combination.

The release agent layer is usually a resin such as those mentioned above,
Wax or the like is dissolved in an appropriate organic solvent to give a solution, which is applied onto the above-mentioned substrate by an appropriate coating means and dried,
Although not limited, the film thickness is usually 0.1 to 1 μm.
It is formed so that Examples of the coating means include a gravure coater, a reverse roll coater, an offset gravure coater, a knife doctor coater, a pipe doctor reverse coater, and a slit reverse roll coater. However, it is not limited to these. This release agent layer facilitates peeling of the transfer layer from the base material when the transfer layer is subjected to thermal transfer printing from the transfer material on the transfer target.

As described above, the first layer is on the release agent layer.
Is provided with a protective layer or a colored layer. Here, the protective layer refers to a colorless, transparent or semitransparent resin layer, and the colored layer refers to a colored transparent or semitransparent resin layer. The film thickness is not particularly limited, but normally, a range of 0.1 to 1 μm is suitable. Such a first protective layer or colored layer may be made of a thermoplastic resin or a thermosetting resin. As such a thermoplastic resin or a thermosetting resin, for example, melamine resin, urea resin, melamine-epoxy copolymer resin, melamine-urea co-condensation resin, melamine-acryl co-condensation resin and other amino resins, acrylic resins, It is made of polyurethane resin, polyester resin, polyamide resin or the like. A solution of these thermoplastic resins or thermosetting resins is applied onto the release agent layer by a conventional method and dried to form a first protective layer or colored layer on the release agent layer. can do.

In the present invention, it is preferable that the first protective layer or the colored layer is composed of a thin film of an active energy ray-curable resin. Since the first protective layer or the coloring layer constitutes the surface of the transfer layer obtained by transferring the transfer material according to the present invention to the transfer target, a thin film made of a thin film of the active energy ray curable resin is used as the first protective layer or the colored layer. By using the protective layer or the colored layer, it is possible to obtain a transfer layer having excellent weather resistance and chemical resistance as well as abrasion resistance and scratch resistance.

Various kinds of active energy ray-curable resins are already known, and any of them can be used in the present invention, but an ultraviolet ray-curable resin or an electron beam-curable resin is preferable. Mold resin is used. As the ultraviolet curable resin, for example, a compound or polymer having an acryloyl group or a methacryloyl group as an ultraviolet active group is preferably used. Examples of such compounds or polymers include methyl acrylate, methyl methacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, polyester acrylate, epoxy acrylate, polyurethane acrylate, polyol acrylate, polyether. An acrylate, an oligo acrylate, an alkyd acrylate etc. can be mentioned. In these ultraviolet curable resins, a polyacrylate as an oligomer and a monomer as a diluent thereof are usually used together. Further, if necessary, a sensitizer, a polymerization initiator, a stabilizer, a filler and the like are used in combination.

On the other hand, examples of electron beam curable resins include unsaturated polyester, polyester acrylate,
Polyacrylates such as epoxy acrylate, polyurethane acrylate, polyether acrylate, melamine acrylate, and polyol acrylate, polyester methacrylate, epoxy methacrylate, polyurethane methacrylate, polyether methacrylate,
Polymethacrylates such as melamine methacrylate and polyol methacrylate, styrene-based monomers such as styrene and α-methylstyrene, acrylic acid esters such as methyl acrylate, methoxyethyl acrylate and butyl acrylate, methyl methacrylate, methacrylic acid ethyl,
Methacrylic acid esters such as propyl methacrylate can be mentioned. These may be used alone or as a mixture.

In addition to the function of protecting the surface of the transfer layer, this first protective layer or colored layer, especially when it is a colored layer, is a transfer material obtained by thermal transfer printing of the transfer material according to the present invention onto a transferred material. In the layer, the see-through iris mixes with the color tone of this colored layer to give a complicated and delicate color tone to the later-described pattern, and also functions as a background for giving a three-dimensional depth.

A transparent or translucent picture pattern layer is formed on the first protective layer or colored layer. The first
The protective layer or colored layer also has the function of an anchor layer for stably forming a pattern layer thereon. This pattern layer is usually formed by printing an arbitrary pattern on the first protective layer or colored layer with a synthetic resin printing ink containing a dye and / or a pigment as a colorant. . The film thickness is not limited, but is usually 0.
The range is from 1 to 5 μm, and the range from 1 to 3 μm is preferable.

The dye or pigment to be used is not particularly limited, and in addition to ordinary dyes, if necessary, for example,
Fluorescent dyes, fluorescent pigments, phosphorescent pigments, extender pigments, pearl pigments, metal powder pigments and the like are also used. Further, the synthetic resin printing ink may be an ordinary bake-curable type or an active energy ray-curable type as described above. Further, the ink may be a temperature indicating ink that reversibly changes color depending on temperature.

A second protective layer or a colored layer made of a transparent or translucent resin layer is formed on the picture pattern layer, and further three layers are formed on the second protective layer. A vapor deposited thin film structure of metal or metal oxide is formed. The second protective layer or the colored layer causes a brushing phenomenon in the vapor-deposited thin film due to residual solvent gas or plasticizer gas released from the pattern layer under vacuum when forming such a vapor-deposited thin film. This is to prevent the above-mentioned phenomenon and enhance the adhesion of the vapor-deposited thin film. As the second protective layer or colored layer, the same resin as the above-mentioned first protective layer or colored layer is used. As with the first protective layer or the colored layer, the film thickness is usually suitable in the range of 0.1 to 1 μm.

In the transfer material according to the present invention, this second
A vapor-deposited thin film structure is formed on the protective layer. This vapor-deposited thin film structure has a reflectance of 15 to 3 on the second protective layer.
5% low reflective metal or metal oxide thin film, refractive index
A low-refractive-index metal oxide vapor-deposited thin film having a refractive index of 0.5 to 2.5 and a high-reflectivity metal vapor-deposited thin film having a reflectance of 75 to 98% are vapor-deposited and laminated in this order.

First, a low-reflectivity metal or metal oxide vapor-deposited thin film having a reflectance of 15 to 35% is formed of chromium, titanium, zinc,
It is selected from cupric oxide, chromium oxide and zinc oxide. For example, the chromium vapor-deposited thin film preferably has a thickness in the range of 30 to 80 Å.

The low refractive index metal oxide or metal fluoride vapor-deposited thin film having a refractive index of 0.5 to 2.5 is composed of silicon monoxide, silicon dioxide, indium oxide, indium tin oxide, titanium oxide, magnesium fluoride and fluorine. It is selected from calcium chloride. Among these, a vapor-deposited thin film made of silicon oxide such as silicon monoxide or silicon dioxide is particularly preferable because it can give a more vivid iris color.

The highly reflective metal evaporated thin film having a reflectance of 75 to 98% is selected from aluminum, tin, nickel, silver and alloys thereof. Such a vapor-deposited thin film is, for example,
It can be formed by a high frequency induction heating method, an electric resistance heating method, a sputtering method, an ion plating method, an electron beam heating vapor deposition method or the like according to a conventional method.

A heat-sensitive adhesive layer is formed on the vapor-deposited thin film structure. The heat-sensitive adhesive is not limited at all, and various thermoplastic resins and thermosetting resins are appropriately used. As such an adhesive, for example, vinyl acetate resin,
Ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, polyamide resin, epoxy resin, polyester resin, phenol resin, petroleum resin, cellulose resin, rosin and various other resins. And derivatives thereof, rubber-based resins, chlorinated olefin resins and the like. The adhesive may contain a filler, if necessary. The thickness of the heat-sensitive adhesive layer is not particularly limited, but is usually 0.5 to 5 μm.
The range of m is appropriate. If necessary, a third protective layer or colored layer 10 is formed on the vapor-deposited thin film structure, and a heat-sensitive adhesive layer is formed thereon.

[0023]

FIG. 2 shows the transfer layer 13 obtained by thermally transferring the transfer material according to the present invention onto the transfer target 12. The operation and effect of the transfer material according to the present invention will be described for this transfer layer.
According to this transfer layer, generally, the film thickness of the low-reflectivity vapor deposition thin film and the metal or metal oxide species constituting it and the film thickness of the low-refractive vapor deposition thin film and the metal or metal oxide species constituting it The color of the light reflected by the low-reflectance vapor deposition thin film (this is referred to as initial reflection) is determined by the combination of, and the complementary color is transmitted through the low-refraction vapor-deposition thin film to obtain the high-reflectance vapor deposition thin film. (Refer to final reflection.) Thus, the iris of two colors is obtained by the initial reflected light and the final reflected light. This iris is seen through together with the colored layer 3 and the pattern layer 4.

Table 1 shows the metal or metal compound species constituting the low-reflectivity vapor-deposited thin film, the low-refraction vapor-deposited thin film and the high-reflectivity vapor-deposited thin film, and the relationship between the film thickness and the iris color tone.

[0025]

[Table 1]

In Table 1, the circle marks of the low-reflectivity vapor deposition thin film and the high-reflectivity vapor deposition thin film indicate the metal or metal compound species which constitutes the vapor deposition thin film structure together with the low refractive index vapor deposition thin film. The low-reflectivity vapor-deposited thin film has a thickness of 30-80 Å for chromium, 50-70 Å for titanium, and 30-80 Å for zinc. The high-reflectivity vapor-deposited thin film has a thickness of 400-500 for aluminum. Angstrom, nickel is 350-450 angstrom and tin is 350-400 angstrom.

For example, the low reflective vapor deposition thin film has a thickness of 30 to 8
When the chrome vapor-deposited thin film of 0 angstrom and the low-refractive-index vapor-deposited thin film is a silicon dioxide vapor-deposited thin film of 800 to 1100 angstrom in thickness, the green component of the incident light is initially reflected, and its complementary pink component is low. Since it passes through the refraction deposited thin film and is finally reflected by the highly reflective deposition thin film, an iris of two colors, green and pink, can be obtained.
The low reflection vapor deposition thin film is a chromium vapor deposition thin film having a film thickness of 30 to 80 Å, and the low refractive vapor deposition thin film is a film thickness of 600.
~ 700 angstrom silicon monoxide vapor deposition thin film, of the incident light, the blue component is initially reflected, its complementary color yellow (gold) component is transmitted through the low refraction vapor deposition thin film, the high reflective vapor deposition thin film. Since it is finally reflected at, it is possible to obtain an iris of two colors of blue and yellow (gold).

As another example, a low-reflectivity vapor deposition thin film has a thickness of 5
When the titanium vapor deposition thin film having a thickness of 0 to 70 angstrom and the low refractive index vapor deposition thin film is a silicon monoxide vapor deposition thin film having a film thickness of 1100 to 1300 angstrom, the orange component of the incident light is initially reflected and its complementary color is red. Since the components pass through the vapor deposition thin film having a low refractive index and are finally reflected by the vapor deposition thin film having a high reflectivity, an iris of two colors, orange and red, can be obtained.

As described above, according to the present invention, the film thickness of the low reflective vapor deposition thin film is made constant, and the film thickness of the low refraction vapor deposition thin film is maintained within a constant film thickness range in which each color tone is generated. As a result, it is possible to obtain a bicolor iris having each color tone. On the other hand, according to the present invention, when the film thickness of the low refractive index vapor-deposited thin film is made nonuniform in the width direction or the longitudinal direction of the substrate, or in any other direction, the transfer layer is extremely elegant, beautiful and full of three-dimensional effect. This produces a multicolored or iridescent, highly glittering iris.

The transfer material according to the present invention is, for example, a surface character picture pattern of a cosmetic box, a cover or a reverse character of a book or the like, a plastic panel, a card, a surface character picture pattern of a toy,
It is suitably used as a binder transfer foil base material for textiles and cloths, a transfer material for pulling foil, which is indispensable for weft yarns of Nishijin woven belts, and the like.

[0031]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Parts indicate parts by weight.

Example 1 Polyethylene wax 10 parts, Montan wax 5 parts,
Toluene 30 parts with acrylic resin 20 parts and fluorine resin 5 parts
Parts, 10 parts of acetone, 10 parts of methyl ethyl ketone, 5 parts of methyl isobutyl ketone and 5 parts of ethyl glycol were added and mixed well. This is coated on one side of a transparent polyphenylene sulphide film with a gravure coater and dried at 160 ° C to a thickness of 0.5μ.
m release agent layer was formed.

Next, 30 parts of melamine-urea co-condensation resin,
15 parts of melamine resin, 1 part of curing catalyst p-toluenesulfonic acid, 4 parts of dye "Orazol Yellow" (manufactured by Ciba Geigy) and 2 parts of "Orazol orange" (manufactured by Ciba Geigy), 20 parts of methyl ethyl ketone, A thermosetting resin coating material was prepared by adding to a mixed solvent consisting of 10 parts of diacetone alcohol, 10 parts of methanol and 8 parts of isopropyl alcohol and thoroughly mixing them. This is applied on the release agent layer with a gravure coater, and the temperature is 150 to 160 ° C.
And dried to form a first colored layer having a film thickness of 1 μm.

Then, 5 parts of the dye "Zapon Farst Pink B" (manufactured by BASF), 10 parts of a luminous pigment "Lumilux Green CD101b" (manufactured by Hoechst), and a metal powder pigment (aluminum powder friend color silver F500S).
I (manufactured by Showa Denko KK) 5 parts and Patent No. 688991
No. 5 vacuum-deposited powder, 10 parts polyester acrylate as UV curable resin, 30 parts polyurethane acrylate, 1 trimethylolpropane triacrylate
0 parts and 5 parts of benzoin sensitizer were added to a mixed solvent consisting of 10 parts of methyl ethyl ketone and 10 parts of ethyl acetate,
Printing ink was prepared by thoroughly kneading and mixing.

A gravure pattern was printed on the colored layer using this printing ink, dried at 150 to 170 ° C., and then irradiated with ultraviolet rays from a high pressure mercury lamp (output 30 KW) to give a thickness of 2 A 0.5 μm pattern print layer was formed.

20 parts of polyurethane resin, 1 acrylic resin
5 parts, phenol resin 10 parts and curing agent isocyanate compound 5 parts ethyl acetate 5 parts, methyl ethyl ketone 30 parts
Parts, 10 parts of methyl isobutyl ketone, and 5 parts of toluene were added to the mixed solvent and kneaded and mixed sufficiently. The resin composition thus prepared was applied onto the above-mentioned picture pattern printing layer by a gravure coater and baked and cured at 140 to 160 ° C. to form a second protective layer having a film thickness of 1 μm.

On this second protective layer,
A vapor deposited thin film structure was formed. First, the degree of vacuum is 2.5 × 10 ^-4
Film thickness 30-80 by electron beam evaporation method under vacuum of Toll
A low-reflectance vapor-deposited thin film made of an angstrom chromium metal vapor-deposited thin film was formed at a speed of 150 m / min. Then
A low-refractive-index vapor-deposited thin film composed of a magnesium fluoride fluoride vapor-deposited thin film was formed on the above-mentioned low-reflectivity vapor-deposited thin film by an electron beam heating vapor-deposition method under a vacuum of 2.5 × 10 ⁻⁴ Torr. When preparing this low-refractive-index vapor-deposited thin film, the vapor-deposition rate was 150 to 2
The film thickness was varied constantly within the range of 00 m / min, and the film thickness was also varied within the range of 500 to 1100 angstroms in the width direction of the substrate to give a non-uniform film thickness.

Finally, a highly reflective evaporated thin film made of a nickel evaporated thin film having a film thickness of 400 Å was formed by electron beam heating evaporation under a vacuum with a vacuum degree of 2.0 × 10 ⁻⁴ Torr.
It was formed on the above-mentioned low refractive index vapor-deposited thin film at a speed of m / min.

After the vapor-deposited thin film structure is laminated in this manner, a third protective layer is formed thereon in the same manner as the second protective layer, and a transparent heat-sensitive adhesive is further formed thereon. The layers were laminated. This heat-sensitive adhesive layer is made of polyester resin 7
Parts, polyamide resin 10 parts, petroleum resin 3 parts and ethylene-vinyl acetate copolymer resin 10 parts, methyl ethyl ketone 20 parts, toluene 20 parts, isopropyl alcohol 15
Parts and 15 parts of methanol, mixed well, mixed well and coated with a reverse roll coater,
The film was dried at 120 to 150 ° C. to have a film thickness of 1.5 μm.

In the transfer material thus obtained, the film thickness of the low-refractive-index vapor-deposited thin film is not uniform, so that a multicolored iris from dark blue to purple to orange to red is produced. This transfer material was subjected to thermal transfer printing on the surface of a transparent ABS resin plate using a thermal transfer machine (Katani Sangyo) at a rubber temperature of 180 ° C. and a dwell time of 2 seconds to form a transfer layer. On the transfer layer, a pattern pattern was three-dimensionally seen through against a background of a colorful iris. In addition, when the transfer layer was irradiated with ultraviolet rays, the pattern was excited to emit light, and the three-dimensional effect was further enhanced, and a brilliant, bright and colorful multicolored iris was seen through.

Further, the friction fastness of the surface of the transfer material was examined by a dyeing fastness tester, and as a result, 500 g with a cloth,
It has been shown to withstand 150 rubs and thus also have excellent abrasion resistance and scratch resistance.

Example 2 10 parts of carnauba wax, 5 parts of synthetic wax, 5 parts of fatty acid amide and 20 parts of styrene resin were mixed with 30 parts of xylene, 15 parts of toluene, 10 parts of diacetone alcohol and 5 parts of methyl glycol. In addition, mixed well. This is applied on one side of a transparent polyimide film with a gravure coater and dried at 150 to 160 ° C.,
A release agent layer having a thickness of 0.5 μm was formed.

Next, 30 parts of polyurethane acrylate,
20 parts of epoxy acrylate and 20 parts of neopentyl glycol diacrylate were added together with 1 part of acetophenone-based sensitizer to a mixed solvent consisting of 19 parts of acetone and 10 parts of ethyl acetate and mixed sufficiently to prepare an ultraviolet curable resin solution. did. This is applied onto the release agent layer with a gravure coater and dried at 150 to 170 ° C., and then a high pressure mercury lamp (output 30 KW, wavelength 250 to 420 n).
m) was used to form a first protective layer having a film thickness of 1 μm.

Then, the dye "The Pon Farst Blue H
FL "(manufactured by BASF) 2 parts, fluorescent pigment" Shin Loihi Color FZ-3045S Lemon Yellow (manufactured by Shin Loihi Co.) 3 parts, acrylic resin 20 parts, melamine-urea co-condensation resin 10 parts, polyurethane polyol 10 parts and isocyanate compound. 5 parts was added to a mixed solvent consisting of 30 parts of methyl ethyl ketone, 5 parts of ethyl cellosolve and 15 parts of xylene, and kneaded and mixed sufficiently to prepare a printing ink.
A picture pattern was gravure printed on the protective layer using this printing ink, and baked and cured at 150 to 170 ° C to form a picture pattern printed layer having a thickness of 20 µm.

As an ultraviolet curable resin, 10 parts of polyethylene acrylate, 30 parts of urethane acrylate and 10 parts of methyl methacrylate and 1 part of acetophenone sensitizer were added to a mixed solvent consisting of 10 parts of acetone, 25 parts of methyl ethyl ketone and 14 parts of ethyl acetate. , Kneaded well. This UV-curable resin composition is applied on the above-mentioned pattern printing layer by a gravure coater, and the temperature is 150 to 170 ° C.
After drying the solvent with a high pressure mercury lamp (output 30K
W, wavelength 250-420 nm) was irradiated with ultraviolet rays to cure and form a second protective layer having a film thickness of 1 μm.

On this second protective layer,
A vapor deposited thin film structure was formed. First, the degree of vacuum is 3.0 to 5.0 x
Film thickness 30 by electron beam heating evaporation method under vacuum of 10 ^-4 Torr
A low-reflectance vapor-deposited thin film consisting of a zinc metal vapor-deposited thin film of -80 angstrom was formed at a speed of 250 m / min. Next, a low-refractive-index vapor deposition thin film consisting of a calcium fluoride vapor-deposited thin film having a thickness of 500 to 600 angstrom was formed by electron beam vapor deposition under a vacuum of 2.5 × 10 ⁻⁴ Torr.
It was formed on the above-mentioned low-reflectivity vapor-deposited thin film at a speed of m / min.
Finally, a highly reflective evaporated thin film consisting of a tin evaporated thin film having a film thickness of 350 angstrom by a one coil rectangular parallelepiped crucible method by a high frequency induction heating evaporation method under a vacuum with a vacuum degree of 2.0 × 10 ⁻⁴ Torr. Was formed on the above-mentioned low refractive index vapor-deposited thin film at a speed of 250 m / min.

Then, a third protective layer is laminated on the vapor-deposited thin film structure in the same manner as the second protective layer, and a heat-sensitive adhesive layer is further formed thereon as follows. did.
That is, 5 parts of vinyl chloride-vinyl acetate copolymer resin, 10 parts of acrylic resin, 5 parts of chlorinated olefin resin and 5 parts of phenol resin were used as the filler, and magnesium carbonate powder 5 was used.
60 parts to 60 to 130 by adding to a mixed solvent consisting of 30 parts of ethyl acetate, 10 parts of acetone and 30 parts of toluene and thoroughly mixed together.
The film was dried at ℃ to a film thickness of 1.5 μm.

The transfer material thus obtained is subjected to thermal transfer printing on a binder-treated cloth product such as polyester tricot, knitted product, woven fabric, non-woven fabric or binder-treated leather product to form a transfer layer. Provided.
The pattern of the transfer layer was seen three-dimensionally with the background of the bichromatic iris of dark blue and purple as the transmission angle changed.

Example 3 1 part of silicone resin, 5 parts of rosin-modified maleic acid resin,
10 parts of cellulose acetate propionate and 25 parts of carnauba wax were added to a mixed solvent composed of 30 parts of xylene, 14 parts of methyl ethyl ketone, 10 parts of acetone and 5 parts of methyl glycol, and mixed sufficiently. This is coated on one side of a transparent polyethylene terephthalate film with a gravure coater and dried at 130 ° C to a thickness of 0.5.
A μm release agent layer was formed.

Next, polyester methacrylate 30
Parts, 20 parts of polyester acrylate and 20 parts of methyl methacrylate together with 1 part of benzophenone-based sensitizer to a mixed solvent consisting of 4 parts of ethyl acetate, 15 parts of methyl ethyl ketone and 10 parts of methyl isobutyl ketone, mixed well, and exposed to ultraviolet light. A curable resin solution was prepared. This is coated on the release agent layer with a gravure coater,
After being dried at ℃, it was cured at a speed of 30 m / min using a high pressure mercury lamp (output 30 KW, wavelength 250 to 420 nm) to form a first protective layer having a film thickness of 1 μm.

Next, 1 part of the dye "Zapon Farst Yellow R" (manufactured by BASF), 1 part of "Zapon Farst Yellow RG" (manufactured by BASF), 5 parts of pearl pigment "Iriodin" (manufactured by Merck), fluorescent Pigment "Fluorescence Sense Yellow 083" (manufactured by BASF) 3 parts, polyurethane resin 15 parts, melamine resin 15 parts and curing agent p-toluene sulfonic acid 4 parts methyl ethyl ketone 31 parts, xylene 10 parts, toluene 10 parts and isopropyl. Add to the mixed solvent consisting of 5 parts of alcohol, knead and mix well,
A printing ink was prepared. A gravure pattern is printed on the protective layer using this printing ink to obtain a pattern of 150 to 170.
It was baked and cured at ℃ to form a picture pattern printed layer having a thickness of 2.5 μm.

Melamine-urea co-condensation resin (50% solution)
30 parts, melamine-acrylic copolymer resin (50% solution) 10 parts, melamine resin (50% solution) and curing agent p
-Toluenesulfonic acid 6 parts to methyl ethyl ketone 30
Parts, 10 parts of methyl isobutyl ketone and 10 parts of isopropyl alcohol were added to the mixed solvent and kneaded and mixed sufficiently. This was applied onto the above-mentioned picture pattern printed layer with a gravure coater and baked and cured at 150 to 170 ° C to form a second protective layer.

On this second protective layer,
A vapor deposited thin film structure was formed. First, the degree of vacuum is 2.5 × 10 ^-4
Film thickness 50-70 by electron beam evaporation method under vacuum of Toll
A low-reflectivity vapor-deposited thin film made of an angstrom titanium metal vapor-deposited thin film was formed at a speed of 200 m / min. Then
A low-refraction deposition thin film consisting of a silicon monoxide deposition thin film having a film thickness of 1100 to 1300 angstroms is formed by electron beam heating deposition under a vacuum of a vacuum degree of 2.0 × 10 ⁻⁴ to 100 m / m 2.
It was formed on the above-mentioned low-reflectivity vapor-deposited thin film at a rate of minutes. Finally, a high-reflectivity vapor-deposited thin film made of an aluminum vapor-deposited thin film having a thickness of 400 angstrom was formed by a high-frequency induction heating vapor deposition method under a vacuum of a vacuum degree of 2.0 × 10 ⁻⁴ Torr at a speed of 400 m / min to obtain the low refractive index It was formed on the vapor-deposited thin film.

After the vapor-deposited thin film structure was laminated in this manner, a third protective layer was formed in the same manner as the first protective layer, and a transparent heat-sensitive adhesive layer was laminated thereon. This heat-sensitive adhesive layer is a mixture of 20 parts of acrylic resin, 20 parts of vinyl chloride-vinyl acetate copolymer resin, 5 parts of phenol resin and 5 parts of rubber-based resin, consisting of 10 parts of ethyl acetate, 30 parts of toluene and 10 parts of methyl ethyl ketone. In addition to the solvent,
Mix well and apply this with a gravure coater.
It was dried at 20 to 150 ° C. to have a film thickness of 1.5 μm.

The transfer material thus obtained was subjected to thermal transfer printing on the surface of a transparent ABS resin plate as described above.
According to the obtained transfer layer, the fluorescent gold pearl color pattern could be seen through with a stereoscopic effect against the background of the iris of two colors of orange and red.

Further, as a result of examining the friction fastness of the surface of the transfer material with a dyeing fastness tester, 500 g with a cloth,
It has been shown to withstand 200 rubs and thus have excellent abrasion resistance and scratch resistance.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view of an essential part showing an iris transfer material as one embodiment of the present invention.

FIG. 2 is an enlarged cross-sectional view showing a transfer layer obtained by transferring the transfer material of FIG. 1 onto a transfer target.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Release agent layer 3 ... 1st protective layer or coloring layer 4 ... Picture pattern layer 5 ... 2nd protective layer or coloring layer 6 ... Vapor deposition thin film structure 7 ... Low reflective vapor deposition thin film 8 ... Low refraction vapor deposition thin film 9 ... High reflective vapor deposition thin film 10 ... Third protective layer or colored layer 11 ... Thermosensitive adhesive layer 12 ... Transfer target 13 ... Transfer layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 15/08 B32B 15/08 H C23C 14/06 C23C 14/06 // B32B 33/00 B32B 33/00 B32B 33 / 00

Claims (4)

[Claims] 1. A release agent layer is provided on a substrate, a transparent or semitransparent protective layer or a colored layer is provided thereon, and chromium is provided thereon.
A low-reflectivity metal or metal compound vapor-deposited thin film having a reflectance of 15 to 35% selected from titanium, zinc, cupric oxide, chromium oxide, and zinc oxide, silicon monoxide, silicon dioxide, indium oxide, indium tin oxide, and oxidation. Refractive index selected from titanium, magnesium fluoride and calcium fluoride
0.5-2.5 low-refractive-index metal oxide or metal fluoride vapor-deposited thin film and high-reflectivity metal vapor-deposited thin film having a reflectance of 75-98% selected from aluminum, tin, nickel, silver and alloys thereof. And a transparent or semi-transparent protective layer or a coloring layer and a heat-sensitive adhesive layer in this order. Iris transfer material. 2. The iris transfer material according to claim 1, wherein the protective layer or the colored layer is a thin film made of an active energy ray curable resin. 3. The metal oxide or metal fluoride compound vapor-deposited thin film having a low refractive index is made non-uniform in thickness.
The iris transfer material described. 4. A release agent layer is provided on a substrate, a first transparent or semitransparent protective layer or a colored layer is provided thereon, and a transparent or semitransparent picture pattern layer and a transparent layer are provided thereon. 4. An iris transfer material according to claim 1, further comprising a semi-transparent second protective layer or a colored layer in this order, and a low-reflectivity metal or metal compound vapor-deposited thin film thereon. .