JPS646292B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to gold and silver threads with excellent sulfidation resistance and sweat resistance. [Prior Art] Conventionally, a flat gold and silver thread is obtained by slitting a film-like material in which a vapor-deposited layer of pure silver is provided on a support such as a flexible synthetic resin film or paper, and this flat gold and silver thread is further formed into a core thread ( For example, twisted gold and silver threads made by twisting rayon, nylon, Tetron threads, etc.) are known. [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 (for example, hot-flow rubber), and the silver luster is lost and the layer turns yellow. or change to black. For this reason, gold and silver threads using a vapor-deposited layer of pure silver and articles to which these are applied have the drawback 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 resin top coat layer 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 time goes on, discoloration will gradually occur. Recently, indium has been added on top of the silver vapor deposited layer.
Attempts have been made to improve the sulfidation resistance of the silver deposited layer by providing a thin film of tin, gallium, silicon, etc., or by mixing these metals into the silver deposited layer (for example, 51
-20230, Japanese Patent Publication No. 52-47790, and Japanese Patent Application Laid-Open No. 52-123474). 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 has an even worse problem of poor sweat resistance. . 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 deposited layer or the amount of iridium that can be mixed in, which can improve sulfidation resistance without impairing the inherent luster of the material. ,
We have now completed the present invention by discovering the new fact that it has excellent sulfurization resistance and sweat resistance, and can maintain silver luster for a long period of time. [Means for Solving the Problems] The present invention provides: (1) On one or both sides of a narrow and long flexible substrate,
a silver vapor deposited layer and at least one layer directly in contact with the silver vapor deposited layer;
a gold and silver thread characterized by having an iridium vapor-deposited layer, and (2) a narrow and long flexible substrate on one or both sides of the
The present invention relates to a gold-silver thread characterized by having a vapor-deposited layer made of a substantially uniform mixture of silver and iridium. [Example] The gold and silver thread of the present invention is a metal evaporated laminate (hereinafter referred to as a metal evaporated laminate), which is formed by providing a silver evaporation layer and at least one iridium evaporation layer in direct contact with the silver evaporation layer on one or both sides of a flexible substrate. body (),
Alternatively, it can be obtained by slitting a metal vapor deposited laminate (hereinafter referred to as metal vapor deposited laminate), which is formed by providing a vapor deposited layer made of a substantially uniform mixture of silver and iridium on one or both sides of the substrate. In the above, a vapor deposited layer consisting of a substantially uniform mixture of silver and iridium is a vapor deposited layer in which silver and iridium are in at least one of a metal mixture, an alloy, and a mixture of a metal mixture and an alloy. Refers to a vapor deposited layer. The vapor deposited layer herein includes any metal thin film formed by vacuum vapor deposition, sputtering, and ion plating. Metal evaporated laminate () is one in which a silver evaporated layer and an iridium evaporated layer are provided in this order on one or both sides of a base [metal evaporated laminate a], and one in which an iridium evaporated layer and a silver evaporated layer are provided on one or both sides of a base. There are three types of embodiments: one in which an iridium evaporated layer, a silver evaporation layer, and an iridium evaporation layer are provided in this order on one or both sides of a substrate [metal evaporation laminate c]. . These metal vapor-deposited laminates a, b, and c exhibit a silver luster color when viewed from either the front or back side when the base is transparent or semitransparent, and when viewed from the opposite side when the base is opaque. That is. In metal deposited stacks, the thickness of the iridium deposited layer can vary over a wide range from 5 to 200 Å. If the thickness of the iridium vapor deposited layer is less than 5 Å, the sulfidation resistance will be poor and the silver vapor deposited layer will discolor, which is undesirable. On the other hand, if it exceeds 200 Å, the metallic luster inherent to silver will be hindered by the metallic luster of the iridium vapor deposited layer itself, which is undesirable. . In the present invention, since the allowable range of the thickness of the iridium vapor deposited layer is as wide as the former, process control of the vapor deposition process is very easy. By the way, in the case of conventionally used indium, tin, gallium, and silicon, the allowable range of thickness of the deposited layer of these metals, which can improve the sulfidation resistance without interfering with the metallic luster inherent in the silver deposited layer, is 16. ~50Å, 5~40Å, 5~40Å
The thickness is very narrow, ranging from 20 to 60 Å, making it extremely difficult to control the deposition process. There is no particular limit to the thickness of the silver vapor deposited layer, but it is usually 500 mm thick.
Selected from the range of ~1500 Å. The thickness of the silver deposited layer is
If it is less than 500 Å, the light transmittance will be high,
It is difficult to obtain the metallic luster inherent to silver, and if the thickness exceeds 1500 Å, the film becomes excessively thick, which is not preferable from the viewpoint of resource conservation. In the metal vapor deposited laminate (), the ratio of silver to iridium in the vapor deposited layer consisting of a substantially uniform mixture of silver and iridium is varied over a wide range from 100:0.5 to 100:60 (weight ratio, the same applies hereinafter). It's watery. If the proportion of iridium is less than 0.5, sulfidation resistance will be poor and discoloration of the deposited layer will occur, which is undesirable, while if the proportion of iridium exceeds 60, the metallic luster inherent to silver will be lost, which is not preferable. 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 100:0.5 to 100, which can improve sulfidation resistance without interfering with the metallic luster inherent to silver. :7, which is very narrow, making process control of the vapor deposition process very difficult. The thickness of the deposited layer is not particularly limited, but is usually selected from a range of 500 to 1500 Å. If the thickness of the deposited layer is less than 500 Å, the light transmittance will be high and it will be difficult to obtain the metallic luster inherent to silver, and if it exceeds 1500 Å, the film will be excessively thick, which is undesirable from the viewpoint of resource conservation. There are no particular restrictions on the flexible substrate in the metal vapor deposited laminates () and (), and examples thereof include polyester, polyamide, polyamideimide, polyethylene, polypropylene, polycarbonate,
Any film-like material, sheet-like material, cellophane, paper, etc. made of resin such as polyvinyl chloride or cellulose acetate can be used. Metal vapor deposited laminate ()
If a silver luster color is desired on both the substrate side and the opposite side of the substrate in (), a transparent substrate is used. If a matte silver luster color is desired, a translucent substrate may be used. In the case of a substrate having poor adhesion to the vapor deposited layer, such as a polypropylene film, or in the case of a substrate having an uneven surface, such as paper, it is preferable to previously provide an undercoat layer as a non-coating agent on the substrate. In the metal vapor-deposited laminates () and (), the vapor-deposited layer itself has low mechanical strength and is particularly susceptible to severe damage due to friction, so it is usually preferable to provide a top coat layer as a protective layer on the vapor-deposited layer. As the undercoat layer and the topcoat layer, coating layers of resins such as acrylic resin, urethane resin, urea-melamine resin, epoxy resin, aminoalkyd resin, nitrocellulose, etc., singly or in a blend, are used. Further, in the case of a substrate having poor adhesion to the vapor deposited layer, a coating layer of an anchoring agent such as alkyl titanate may be used as an undercoat layer. The topcoat layer and the undercoat layer when the substrate is transparent or translucent may be colored with a coloring agent such as a paint or pigment. In such a case, various tones of silver luster colors can be obtained. The metal vapor-deposited laminate () is prepared by providing an undercoat layer on one or both sides of the substrate, if necessary, and then sequentially providing a silver vapor-deposited layer and an iridium vapor-deposited layer, or sequentially providing an iridium vapor-deposited layer and a silver vapor-deposited layer. Alternatively, it can be easily obtained by sequentially providing three iridium-deposited layers, a silver-deposited layer and an iridium-deposited layer, and, if necessary, further providing a top coat layer. Any conventional thin film forming method such as a vacuum evaporation method, a sputtering method, or an ion plating method can be employed to form the silver evaporation layer and the iridium evaporation layer. For thin film formation conditions, for example, in the case of vacuum evaporation, a degree of vacuum in the range of 3 x 10 ^-4 to 1 x 10 ^-6 Torr and an evaporation source temperature in the range of 1000 to 3000°C are appropriately adopted depending on the type of metal to be deposited. be done. The metal vapor-deposited laminate () is produced by providing an undercoat layer on one or both sides of the substrate, if necessary, and (1) co-evaporating silver and iridium (for example, heating and evaporating two evaporation sources separately). mosquito,
or (2) it can be easily obtained by vapor depositing an alloy of silver and iridium to provide a vapor deposited layer consisting of a substantially uniform mixture of silver and iridium, and if necessary further providing a top coat layer. 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 plating method can be employed. For example, in the case of a vacuum evaporation method, the thin film forming conditions include a degree of vacuum in the range of 3 x 10 ^-4 to 1 x 10 ^-6 Torr so that the ratio of silver to iridium in the resulting evaporated layer falls within the desired range. The temperature of the evaporation source of silver and iridium is appropriately selected from the range of 1000 to 3000°C. Any of the above-mentioned thin film forming methods can be employed 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 resulting evaporated layer to a desired range. A mixture of silver and iridium may be used instead of the alloy. Sputtering is usually 5.0×
It is carried out in an argon gas atmosphere in the range of 10 ^-2 to 1.0 x 10 ^-3 Torr. The gold and silver thread of the present invention can be obtained by cutting the metal vapor-deposited laminates () and () obtained above into elongated bodies having a width of about 0.15 to 3.0 mm using a slitter or the like. The gold and silver thread obtained in this way is a flat gold and silver thread, but this is further made into rayon,
Twisted gold and silver threads may be obtained by twisting with core threads such as Tetoron and nylon threads. The gold and silver thread 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. Ru. For example, it is used as a gold rand or woven into kimono, obi, and zori. Next, the present invention will be described with reference to reference examples, comparative reference examples, and examples. Reference example 1 Silver is deposited on a 12μ thick polyethylene terephthalate film at 1.0×10 ^-4 Torr and evaporation source temperature 1400℃.
vacuum evaporated to a thickness of 800 Å, and on top of that, iridium was deposited at ^1.0
A metal evaporated laminate was obtained by vacuum evaporation on a mixture of .ANG. (this will be referred to as sample A). An alcohol-toluene solution of urea-melamine resin was further applied onto the iridium vapor-deposited layer of Sample A, and dried to provide 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. For the hydrogen sulfide test, the sample is heated to 20℃, RH95%,
This was done by leaving it in an atmosphere with a hydrogen sulfide concentration of 0.6% for 80 hours. Artificial sweat test is JIS
Conducted in accordance with Law LO848A-1. Appearance evaluation was performed by observing gloss and discoloration on the opposite side of the polyethylene terephthalate film. Appearance evaluation was performed using the following 5-level evaluation. Evaluation value 5 Very good 4 Good 3 Fairly good 2 Fairly poor 1 Poor The results are shown in Table 1. Reference Example 2 A urethane resin cellosolve acetate-ethyl acetate-toluene solution (solid content 20% by weight) was applied onto Japanese paper weighing 19 g, dried to form an undercoat layer, and then silver was applied at 2.0×10 ^-4 torr, Vacuum evaporated to a thickness of 600 Å at an evaporation source temperature of 1500°C, and further deposited iridium at an evaporation source temperature of 2.0×10 ^-4 Torr.
A metal evaporated laminate was obtained by vacuum evaporation at 3000°C to a thickness of 50 Å (this will be referred to as sample A). On top of the iridium vapor deposited layer of sample A, an epoxy resin methyl ethyl ketone-ethyl acetate-
An alcohol solution was applied and dried to provide a top coat layer with a dry thickness of 0.3 μm (this will be referred to as Sample B). 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 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 Å (however, 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. Reference Example 4 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 200 Å (however, 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 in Reference Example 1, except that indium was vacuum-deposited in place of iridium to a thickness of 10 Å at 1.0×10 ^-4 Torr and evaporation source temperature of 1100°C (however, the top coat layer omission). The appearance of the obtained sample was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1. Comparison reference example 2 1.0×10 ^-4 Torr of tin instead of iridium,
A metal evaporated laminate was obtained in the same manner as in Reference Example 1 except that the vacuum evaporation was carried out to a thickness of 100 Å at an evaporation source temperature of 1500°C (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 3 A metal vapor-deposited laminate was obtained in the same manner as in Reference Example 2 except that the iridium vapor-deposited layer was omitted (Sample A was the one without the top coat layer, and Sample B was the one with the top coat layer). 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 1.

[Table] Reference Example 5 Iridium was vacuum-deposited to a thickness of 20 Å on a polyethylene terephthalate film with a thickness of 12μ at a temperature of 1.0×10 ^-4 Torr and an evaporation source temperature of 3000°C, and silver was then evaporated at a thickness of 1.0×10 ^-4 Torr. 1000 at source temperature 1400℃
A metal evaporated laminate was obtained by vacuum evaporation to a thickness of Å (this will be referred to as sample A). An alcohol-toluene solution of urea-melamine resin was further applied onto the iridium vapor-deposited layer of Sample A, and dried to provide a top coat layer with a dry film thickness of 0.5 μm (this will be referred to as Sample B). The appearance of the obtained samples A and B was evaluated 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 A metal evaporated laminate was obtained in the same manner as in Reference Example 5, except that gallium was vacuum-deposited in place of iridium to a thickness of 20 Å at 1.0×10 ^-5 Torr and an evaporation source temperature of 1200°C. The sample without a top coat layer is Sample A, and the sample with a top coat layer is Sample B). 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 2.

[Table] Reference example 6 Iridium 1.0×10 ^-4 Torr on a 12μ thick polyethylene terephthalate film, evaporation source temperature
Vacuum evaporation was performed at 3000°C to a thickness of 5 Å, and then silver was vacuum evaporated to a thickness of 600 Å at 1.0 × 10 ^-4 Torr and evaporation source temperature 1400°C, and on top of that, iridium was deposited to a thickness of 5 Å under the same conditions as above. A metal evaporated laminate was obtained by vacuum evaporation (this will be referred to as sample A). An alcohol-toluene solution of urea-melamine resin was further applied onto the iridium vapor-deposited layer of Sample A, and dried to provide a top coat layer with a dry film thickness of 0.5 μm (this will be referred to as Sample B). The appearance of the obtained samples A and B was evaluated in the same manner as in Reference Example 1. The results obtained are shown in Table 3. Reference Example 7 Silver was deposited on a 12μ thick polyethylene terephthalate film under a vacuum of 1.0×10 ^-4 Torr at an evaporation source temperature of 1500℃ and iridium was deposited at an evaporation source temperature of 3000℃.
A metal evaporated laminate was obtained by simultaneously vacuum evaporating from two crucibles (evaporation sources, the same shall apply hereinafter) at ℃ to provide a 1000 Å thick evaporated layer with a ratio of silver and iridium of 100:1 (this was sample A). ). An alcohol-toluene solution of urea-melamine resin was further applied onto the vapor deposited 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 Reference Example 1. The results are shown in Table 3. Reference Example 8 Under a vacuum degree of 1.0×10 ^-4 Torr, silver was vacuum evaporated at an evaporation source temperature of 1500°C and iridium was simultaneously vacuum evaporated from two crucibles at an evaporation source temperature of 3000°C to a thickness of 1000°C.
A metal vapor-deposited laminate was obtained in the same manner as in Reference Example 7 except that a vapor-deposited layer with a ratio of silver and iridium of 100:20 was provided (Sample A was the one without the top coat layer, Sample A was the one with the top coat layer). B). 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 (100:60) was deposited 5.0x on a 12μ thick polyethylene terephthalate film.
Input power in argon gas atmosphere of 10 ^-3 Torr
1000Å thick by high frequency sputtering at 2.0KW.
A vapor deposited layer with a ratio of silver and iridium of 100:60 was provided to obtain a metal vapor deposited laminate. 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 degree of 1.0×10 ^-4 Torr, silver was vacuum-deposited 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 to a thickness of 1000 Å.
A metal vapor-deposited laminate was obtained in the same manner as in Reference Example 7, except that a vapor-deposited layer with a ratio of silver to silicon of 100:20 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] Example Each of the metal vapor-deposited laminates obtained in Reference Examples 1 to 9 was cut into 0.3 mm width pieces using a slitter to obtain metal threads. All of the obtained gold and silver threads had a beautiful silver luster and did not change color even after a long period of time.

Claims (1)

[Claims] 1. On one or both sides of a narrow and long flexible substrate,
A gold and silver thread comprising a silver vapor deposited layer and at least one iridium vapor deposited layer in direct contact with the silver vapor deposited layer. 2. The gold and silver thread according to claim 1, wherein the iridium vapor deposited layer has a thickness in the range of 5 to 200 Å. 3. The gold and silver thread according to claim 1, wherein the silver vapor deposited layer has a thickness in the range of 500 to 1500 Å. 4. The gold and silver thread according to claim 1, further comprising a top coat layer on the outermost vapor deposited layer. 5 On one or both sides of a narrow and long flexible substrate,
A gold-silver thread characterized by having a vapor-deposited layer consisting of a substantially uniform mixture of silver and iridium. 6 The ratio of silver and iridium is 100:0.5 by weight
Gold and silver thread according to claim 5 in the range of ~100:60. 7. The gold and silver thread according to claim 5, wherein the vapor deposited layer has a thickness in the range of 500 to 1500 Å. 8. The gold and silver thread according to claim 5, further comprising a top coat layer on the vapor deposited layer.