JPS6189100A - Transfer foil - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a transfer foil with excellent sulfidation resistance and sweat resistance.

[Prior Art] Transfer foils have heretofore been known in which a peeling film 1viFF4, a resin layer, a vapor-deposited layer of pure silver, and an adhesive layer are provided in this order on a support such as a flexible synthetic resin film or paper.

[Problems to be Solved by the Invention] However, the vapor-deposited layer of pure silver tends to generate silver sulfide when it comes into contact with hydrogen sulfide gas in the atmosphere or sulfur-containing substances (such as vulcanized rubber), and the silver luster is lost and the layer turns yellow. or change to black. For this reason, transfer foils using a vapor-deposited layer of pure silver and articles to which they are applied have the disadvantage that their commercial value is significantly reduced during storage.

In order to eliminate this drawback, it would be possible to replace the vapor-deposited layer of silver with a vapor-deposited layer of aluminum or other material that does not easily react with sulfur, but the unique luster of silver has been used in various high-class ornaments since ancient times. This depth and soft luster cannot be achieved with other metals.

Therefore, various attempts have been made to use a deposited layer of silver without losing its characteristic metallic luster. One method is to provide a top coat layer made of resin on top of the silver vapor deposited layer, but since such a top coat layer is breathable, it has the effect of preventing discoloration of the silver vapor deposited layer for a short time, but over time. As it ages, discoloration will occur gradually. Recently, it has been reported that the sulfidation resistance of the silver deposited layer can be improved by adding metals such as indium, tin, gallium, silicon, etc. to the silver deposition layer, or by mixing these metals into the silver deposited layer. (For example, Japanese Patent Publication No. 51-20230, Japanese Patent Publication No. 52-47790, and Japanese Unexamined Patent Publication No. 52-123)
(See Publication No. 474).

However, when using the above-mentioned metals, in order to improve sulfidation resistance without impairing the silver-white luster inherent to the silver vapor-deposited layer, the thickness of the thin film of these metals formed on the silver vapor-deposited layer or the silver vapor-deposited layer must be adjusted. It is necessary to control the ratio of these metals mixed in within a very narrow range, which makes process control extremely difficult, and indium also has the problem of generally poor sweat resistance. be.

However, as a result of extensive research by the present inventors in order to overcome the above-mentioned problems, we found that when an iridium vapor deposition layer is provided on the silver vapor deposition layer or when iridium is mixed into the silver vapor deposition layer, the silver vapor deposition layer It has an extremely wide tolerance range for the thickness of the iridium vapor deposited layer or the amount of iridium that can be mixed in, which can improve the sulfidation resistance without impairing the inherent luster. The present invention was completed based on the completely new discovery that it has excellent sulfidation resistance and sweat resistance, and that silver luster can be maintained for a long period of time.

Means for Solving the Problems] That is, the present invention provides: (1) A release layer, a silver vapor deposited layer, at least one iridium vapor deposited layer in direct contact therewith, and an adhesive layer on one side of a flexible substrate. A transfer foil characterized in that it is provided in this order (hereinafter, this transfer foil is referred to as a transfer foil (silver)); The present invention relates to a transfer foil (hereinafter, this transfer foil will be referred to as Transfer i TIII) characterized in that a vapor deposited layer and an adhesive layer are provided in this order.

[Example] In the above, a vapor deposited layer made of a substantially uniform mixture of silver and iridium means that silver and iridium are in at least one of a metal mixture, an alloy, and a mixture of a metal mixture and an alloy in the vapor deposition layer. Refers to a vapor-deposited layer such as that shown in

Further, the vapor deposited layer herein includes any metal thin film formed by vacuum vapor deposition, sputtering, and ion blasting.

In the transfer foil (I), the thickness of the iridium vapor-deposited layer is 5 to 5.
It can vary over a wide range of 200 people. If the thickness of the iridium vapor deposited layer is less than 5, the sulfidation resistance will be poor and the silver vapor deposited layer will discolor, which is undesirable.
If it exceeds 0.00, the metallic luster of the iridium V"j, ?? Fm itself will interfere with the metallic luster inherent in silver, which is undesirable. In the present invention, the allowable range of the thickness of the iridium 8 adhesion layer is wide as described above. The process control of the vapor deposition process is very easy.By the way, in the case of conventionally used indium, tin, gallium and silicon, these metals can improve the sulfidation resistance without interfering with the metallic luster inherent in the silver vapor deposited layer. The acceptable ranges of the thickness of the deposited layer are 16-50, 5-40, 5-40 and 20-6, respectively.
It is very narrow with 0 people, and it is very difficult to manage the deposition process.

The thickness of the silver vapor deposited layer is not particularly limited, but is usually 500 to 15 mm.
Selected from a range of 00 people. The thickness of the silver deposited layer is 500A
If it is less than 1,500, the light transmittance becomes high and it is difficult to obtain the metallic luster inherent to silver, and if it exceeds 1,500, the film becomes excessively thick, which is not preferable from the viewpoint of resource saving.

In the transfer foil (II), the ratio of silver and iridium in the vapor deposited layer consisting of a substantially uniform mixture of silver and iridium can be varied over a wide range from ioo:o, s to ioo:eo <weighting, the same applies hereinafter). It's Chino. If the ratio of iridium is less than 0.5, sulfidation resistance will be poor and discoloration of the deposited layer will occur, which is undesirable.On the other hand, if the kj ratio of iridium exceeds 60, metallic light '+f' peculiar to silver will occur.
I don't like it when 2 is lost. In the present invention, since the mixing ratio of iridium is wide as described above, the process control of the vapor deposition process is easy. By the way, in the case of conventionally used indium, tin, gallium, and silicon, the permissible mixing ratio of these metals to silver is 100:0, which improves sulfidation resistance without interfering with the metallic luster inherent to silver.
．． It is extremely narrow, ranging from 5 to 100 degrees, making it extremely difficult to control the steaming process.

The thickness of the vapor deposited layer is not particularly limited, but is usually 500 to 150 mm.
Selected from a range of 0 people. If the thickness of the vapor-deposited layer is less than 500 layers, the light transmittance will be high and it will be difficult to change the metallic luster inherent to silver, and if it exceeds 1,500 layers, it will be excessive, which is preferable from the viewpoint of resource saving. do not have.

The flexible substrate for transfer foil (1) and (Ill) may be any material that can transfer the transfer layer (peel layer + vapor deposition layer + adhesive layer) onto the transferred object by printing pressure or heat of printing pressure. For example, films and sheets of resins such as polyester, polyamide, polyamideimide, polyethylene, polypropylene, polycarbonate, polyvinyl chloride, cellulose acetate, cellophane,
Paper, synthetic film-like materials, and sheet-like materials are all used.

As the release layer and the adhesive layer, any of those used in conventional transfer foils can be used.

As the release layer, a coating layer of modified phenolic resin, acrylic resin, nitrocellulose, maleic acid resin, cellulose, silicone, rosin, wax, or the like is used. The adhesive layer can be either pressure-sensitive or heat-sensitive; for example, a coating layer of acrylic acid ester-vinyl chloride copolymer, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, etc. is used. .

When the transfer layer is transferred to the object to be transferred, peel it off.
The layer becomes a layer that protects the vapor deposited layer, but if the peeled Nt layer does not serve as a protective layer, peeling and vapor cracking occur.
A resin layer may be provided between the two layers.

As such a resin layer, a coating layer of resins such as acrylic resin, urethane resin, urea-melamine resin, epoxy resin, aminoalkyd resin, nitrocellulose, etc. alone or in a blend is used. The resin layer or release layer may be colored with a colorant such as a dye or pigment as long as they are transparent or translucent. In such cases, various tones of silver luster can be used.

The transfer foil of the present invention has a release layer on one side of the flexible base,
If necessary, provide a resin layer, and then (1) sequentially provide an iridium deposited layer and a silver deposited layer, or f211! Should a vapor-deposited layer and an iridium-deposited layer be provided sequentially, or (3) an iridium-deposited layer, a silver-deposited layer, and an iridium-deposited layer? ? (4) by providing a vapor-deposited layer consisting of a substantially uniform mixture of silver and iridium, and further providing an adhesive layer.

For the formation of the silver vapor deposited layer and the iridium vapor deposited layer in the transfer foil (Il), any ordinary thin film forming method such as a vacuum vapor deposition method, a sputtering method, or an ion blating method can be adopted.As the thin film forming conditions, for example, vacuum vapor deposition 3 x 10 to 1 x 10' depending on the type of deposited metal
A degree of vacuum in the range of 1,000 torr and an evaporation source temperature in the range of 1,000 to 3,000° C. are appropriately employed.

The vapor-deposited layer consisting of a substantially uniform mixture of silver and iridium in the transfer foil (1) can be formed by (1) simultaneous vaporization of silver and iridium (for example, by heating and evaporating two evaporation sources separately), or ( It is formed by depositing an alloy of silver and iridium.

In order to simultaneously deposit silver and iridium, any conventional thin film forming method such as a vacuum evaporation method, a sputtering method, or an ion blating method can be employed.

The thin film forming conditions include, for example, in the case of vacuum evaporation, silver is deposited at a degree of vacuum in the range of 3 x 10' to I x 10' torr so that the ratio of silver and iridium in the resulting vapor deposited layer falls within the desired range. The evaporation source temperature of and iridium is appropriately selected from the range of 1000 to 3000°C.

Any of the above-mentioned layer forming methods can be used when depositing an alloy of silver and iridium. For example, in the vacuum evaporation method, it is preferable to use an electron beam as a heating means for the evaporation source, and the sputtering method is particularly preferable since it is easy to adjust the ratio of silver and iridium in the obtained FAnFfJ to a desired range.

A mixture of silver and iridium may be used instead of the alloy. Sputtering is usually done in 5. OX 10'~1. OX
It is carried out in an argon gas atmosphere in the range of 10-3 Torr.

The transfer knit of the present invention has extremely excellent sulfurization resistance and sweat resistance, and the metallic luster peculiar to silver does not discolor, so it can be extremely advantageously applied to various decorative applications where the metallic luster peculiar to silver is desired. be done. For example, for the production of labels, name plates, marks, etc., Christmas cards, cosmetic packaging, posters, weekly magazines, pH 1 albums, sandals, etc.
Used for decoration of nameplates, various plastic molded products, fabrics, etc.

Next, the present invention will be described with reference to reference examples, reference comparative examples, and examples.

Reference Example 1 Silver was vacuum-deposited on a polyethylene terephthalate film with a thickness of 12 μm to a thickness of 800 mm at a temperature of 1.0×10−4 Torr and an evaporation source temperature of 1400°C, and on top of that, iridium was deposited at a thickness of 800 μm at a temperature of 1.0×10−4 Torr and an evaporation source temperature. 10 at 3000℃
A metal evaporated laminate was obtained by vacuum evaporation to a thickness of about 100 yen (this will be referred to as sample A).

An alcohol-toluene solution of urea-melamine resin was further coated on the iridium vapor-deposited layer of Sample A, and dried to form a top coat layer with a dry film thickness of 0.5 μm (this will be referred to as Sample B).

The resulting samples A and B were evaluated for their appearance immediately after production and after a hydrogen sulfide test and an artificial sweat test.

The hydrogen sulfide test was conducted by leaving the sample in an atmosphere with a temperature of 20°C, RH of 95%, and hydrogen sulfide concentration of 0.6x for 80 hours. Artificial sweat test is JISLO848A-
This was done in accordance with the 1st law.

Appearance evaluation was performed using I! gloss and discoloration on the opposite side of the polyethylene terephthalate film. l! This was done by F. Appearance evaluation was performed using the following 5-level evaluation.

Evaluation value 5 Very good 4 Good Good 3 Somewhat good 2 Slightly poor 1 Bad Good The results are shown in Table 1.

Reference Example 2 Urethane resin cellosolve acetate-ethyl acetate-toluene solution (solid content 20% nail stitching) was placed on Japanese paper weighing 19 g.
) was coated and dried to form undercoat debris, and then silver was applied at 2.0 x 10-4 torr and evaporation source temperature at 1500°C.
Vacuum evaporation was carried out on the surface of 600 people, and 2 more layers of iridium were added.
．． OX 10-4 Thor, evaporation source) A metal thermal R4 laminate was obtained by vacuum evaporation at 3000℃ to a thickness of 50 mm (
This will be referred to as sample A).

A methyl ethyl ketone-ethyl acetate-alcohol solution of engineered boxy resin was further applied to the iridium of sample △ and then dried to form a top coat layer with a dry film thickness of 0.3 μm (this was referred to as sample B). do).

The appearance of the obtained Samples A and 2 was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

Reference Example 3 A metal vapor-deposited laminate was obtained in the same manner as in Reference Example 1, except that the thickness of the iridium vapor-deposited layer was changed to 100 (but the top coat layer was omitted).

Table 1 shows the five results of appearance evaluation of the obtained samples in the same manner as the reference PAI.

Reference Example 4 A metal vapor deposited laminate was obtained in the same manner as Reference Example 1 except that the thickness of the iridium vapor deposited layer was changed to 200 (but the top coat layer was omitted).

The appearance of the obtained sample was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

Comparative Reference Example 1 A metal evaporated laminate was obtained in the same manner as Reference Example 1, except that indium was vacuum-deposited in place of iridium at 1.0 xiO-4 Torr and at an evaporation source temperature of 1100°C to a thickness of 10 mm. −Sub coat layer omitted>.

Appearance rPI of the obtained sample was determined in the same manner as in Reference Example 1.
I did ilj. The results are shown in Table 1.

Comparative Reference Example 2 1. Tin was used instead of iridium. A metal evaporated laminate was obtained in the same manner as in Reference Example 1, except that vacuum evaporation was carried out at 1500° C. to a thickness of 100 mm (however, the top coat was omitted).

The appearance of the obtained sample n was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

Comparative Reference Example 3 A 6-layer metal vapor-deposited body was obtained in the same manner as in Reference Example 2 except that the iridium vapor-deposited layer was omitted. ).

The resulting samples A and B were evaluated for appearance in the same manner as in Reference Example 1 (1).The results are shown in Table 1.

[Margins below] Table 1 Reference Example 5 Iridium was placed on a polyethylene terephthalate film with a thickness of 12μ. OX 10' Tall, evaporation source temperature 3
Vacuum evaporated to a thickness of 20 mm at 000°C, and then deposited 1.0 x 10-4 torr of silver at a source temperature of 1400°C.
A metal evaporated laminate was obtained by vacuum evaporation to a thickness of 0.000 mm (
This will be referred to as sample A).

An alcohol-toluene solution of urea-melamine resin was further applied onto the iridium vaporized NF5 of sample A, and dried to provide a top coat layer with a dry R film thickness of 0.5 μm (this is referred to as sample B).

The resulting samples Δ and B were evaluated for appearance in the same manner as in Reference Example 1. The results obtained are shown in Table 2. In this case, gloss and discoloration on the polyethylene terephthalate film side were observed.

Comparative Reference Example 4 1. Gallium was used instead of iridium. Metal evaporated stacks were obtained in the same manner as in Reference Example 5, except that vacuum evaporation was carried out to a thickness of 20 mm at OX 10-5 Tall and evaporation source temperature of 1200°C (Top-to-1 to smooth ones were Sample A, The one with 1-Tupko-1-1 layer is designated as Test 14 B).

The resulting samples A and B were evaluated for appearance in the same manner as in Reference Example 1 (leather). The results are shown in Table 2.

Table 2 Reference Example 6 Iridium 1. OX 10-41--le, evaporation source temperature 3
Vacuum evaporated to a thickness of 5 mm at 0.000'C and then deposited silver on top. Ox 10-' Torr, evaporation source temperature 14oO℃
Iridium was further vacuum-deposited to a thickness of 600 mm under the same conditions as above to obtain a metal-deposited laminate (this is referred to as Sample A).

An alcohol-toluene solution of urea-melamine resin was further coated on the iridium vaporized layer of Sample A and dried to provide a top coat layer with a dry film thickness of 0.5 μm (this is referred to as Sample B).

The appearance of the obtained Samples A and B was evaluated in the same manner as in S Example 1. The results obtained are shown in Table 3.

Reference Example 7 On a polyethylene terephthalate film with a thickness of 12μ, silver was evaporated at a source temperature of 1500°C and iridium was deposited at 5T (deposition humidity 30°C) under a vacuum of 1.0x10-'Torr.
At 00℃, vacuum evaporation was performed using a crucible (evaporation) with two turns at the same time, and the thickness was 1,000 yen, and the ratio of A and iridium was 100:1. 18 layers and this is called "lA").

An alcohol-toluene solution of urea-melamine resin was further applied on the vapor deposited layer of sample A, and dried until the dry film thickness was 0.
To provide a 5μ top coat layer, refer to this as sample B)
.

The obtained samples Δ and B were given the same IP as Example 1 in Reference 8, and the appearance evaluation was 11. The results are shown in Table 3.

Reference F'+ 8 1.0xlO-' Silver is available as a source under a vacuum degree of 1.0xlO-' 1 Iridium is evaporated at a crystallinity of 1500°C as an evaporation source Irj730
Air steaming from two crucibles at 00℃ at the same time? 1 and thickness 1
ooo person, Gintoirishiu L (!: '7) /1'1
Combined 1fi 100:20 (7:l, i.

The IJ with the anchorage attached was obtained in the same manner as in Example 7.
△, one with a top coat layer is designated as Sample Ii F3).

The appearance of the obtained samples A and B was evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.

Reference Example 9 Silver-iridium alloy (5.0 x 10-
Input power 2, OKW in argon gas atmosphere of 3 torr
A metal vapor deposited laminate was obtained by high frequency sputtering to provide a vapor deposited layer with a thickness of 1000 mm and a ratio of silver to iridium of 100:60.

The appearance of the obtained sample was evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.

Comparative Reference Example 5 Under a vacuum of 1.0 x 10-4 Torr, silver was vacuum-evaporated at an evaporation source temperature of 1500°C and silicon was vacuum-deposited from two crucibles at the same time at an evaporation source temperature of 1500'C. A metal vapor-deposited laminate was obtained in the same manner as in Reference Example 7 except that a vapor-deposited layer having a ratio of 100:20 to silicon was provided.

The appearance of the obtained sample was evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.

Table 3 Example 1: Apply a toluene solution of wax on a 12 μm thick polyethylene terephthalate fin coated cloth, dry it to form a peeling layer with a dry film thickness of 0.1 μm, and apply urea-melamine resin alcohol on top of it. A toluene solution was applied, dried, and a layer of resin with a dry film thickness of 1.0 μm was applied, followed by 1.0 μm of iridium.
Ox 10-4 torr, evaporation source) n degree 20 at 3000℃
Vacuum evaporation is carried out on the width of a person, and silver is successively deposited in 1. OX10
Vacuum deposition was carried out to a thickness of 800 mm at -4 torr and an evaporation source temperature of 1400°C, and then a toluene-ethyl acetate solution of vinyl chloride-vinyl acetate comonomer was coated on top of it at t5 and dried to a dry film thickness of 1.5 μm. A transfer foil was obtained by providing an adhesive layer.

Using the obtained transfer foil, hot stamping was carried out on the tulle according to a conventional method. The transfer layer formed on the paper had a beautiful silver luster and did not change color even when used by Nagatoma R. Katsutoshi.

Claims (1)

[Scope of Claims] 1. A transfer foil characterized in that a release layer, a silver vapor deposition layer, at least one iridium vapor deposition layer in direct contact therewith, and an adhesive layer are provided in this order on one side of a flexible substrate. . 2. The transfer foil according to claim 1, wherein the iridium vapor-deposited layer has a thickness in the range of 5 to 200 Å. 3. The transfer foil according to claim 1, wherein the silver vapor deposited layer has a thickness in the range of 500 to 1500 Å. 4. The transfer foil according to claim 1, further comprising a resin layer on the side opposite to the base of the release layer. 5. A transfer foil characterized in that a release layer, a vapor deposition layer made of a substantially uniform mixture of silver and iridium, and an adhesive layer are provided in this order on one side of a flexible substrate. 6 The ratio of silver and iridium is 100:0.5 by weight
The transfer foil according to claim 5, which has a ratio of 100:60 to 100:60. 7. The transfer foil according to claim 5, wherein the thickness of the vapor deposited layer is in the range of 500 to 1500 Å. 8. The transfer foil according to claim 5, further comprising a resin layer between the release layer and the vapor deposition layer.