JPS6360135B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel gold and silver thread. More specifically, it has excellent stain resistance against dyeing with disperse dyes, sulfur resistance, heat resistance, light resistance, chemical resistance, sweat resistance, solvent resistance, abrasion resistance, alcohol resistance, etc. This invention relates to gold and silver threads that have outstanding physical and chemical properties and that can maintain the original luster and color tone of gold and silver threads. Traditionally, gold and silver threads made by slitting metallized films used in textiles and other applications include (a)
A metal vapor-deposited layer is provided by vapor-depositing aluminum, silver, etc. on one or both sides of a polyester film such as polyethylene terephthalate, and a resin coating is applied on the metal-deposited layer to form an overcoat resin layer, or (b) the above-mentioned A gold and silver thread is used, which is made by slitting two polyester films with a metal vapor deposited layer on one side, which are laminated together with the metal vapor deposited layer on the inside. However, since the outermost layer of these gold and silver threads is composed of a resin coating or resin film, they have stain resistance, sulfurization resistance, heat resistance, light resistance, chemical resistance, sweat resistance, and solvent resistance. However, if the physical and chemical properties such as abrasion resistance and alcohol resistance are insufficient, for example, if the gold and silver threads are woven with undyed polyester fibers and then dyed with disperse dyes, the surface of the gold and silver threads will be coated with a resin coating. Since it is a polyester film, the gold and silver threads themselves are dyed.For example, when dyed with a blue disperse dye, the silver threads become blue and the gold threads become green, and the drawback is that the original metallic luster of the gold and silver threads cannot be maintained. In addition, in the case of gold and silver threads that contain a silver vapor deposited layer, the resin coating or polyester film itself has some air permeability, so over time it will sulfide due to contact with hydrogen sulfide gas or sulfur compounds in the atmosphere. It produces silver and gradually discolors. For this reason, gold and silver threads using a silver vapor deposition layer and woven and knitted fabrics using the same have the disadvantage that their commercial value is greatly reduced during storage or use. In the case of silver thread, aluminum is an amphoteric metal and has poor chemical resistance and is susceptible to discoloration due to oxidation.
Gold and silver threads containing an aluminum vapor-deposited layer and articles to which they are applied have the drawback that their commercial value is significantly reduced during storage or use. However, the inventors of the present invention have conducted various researches in order to eliminate the above-mentioned drawbacks of conventional gold and silver threads.
Even in the case of gold and silver threads that include a vapor-deposited layer of silver or aluminum, they have excellent stain resistance, sulfidation resistance,
Heat resistance, light resistance, chemical resistance, sweat resistance, solvent resistance,
We have succeeded in developing gold and silver thread with significantly improved physical and chemical properties such as abrasion resistance and alcohol resistance. That is, in the present invention, two base films each having a metal vapor deposited layer on one side are laminated with the metal vapor deposited layer on the outside via an adhesive, or two base films are provided with metal vapor deposited layers on both sides of the base film. and a gold and silver thread characterized in that it is a slit thread of a laminate having a structure in which a transparent inorganic metal compound vapor-deposited layer is formed on the metal vapor-deposited layer. The gold and silver thread of the present invention has a structure in which both sides of a conventional gold and silver thread are coated with a transparent inorganic metal compound vapor-deposited layer, and because it is coated with a transparent inorganic metal compound vapor-deposited layer, it is excellent against dyeing with disperse dyes, etc. It has excellent stain resistance, sulfidation resistance, heat resistance, light resistance, chemical resistance, sweat resistance, solvent resistance, abrasion resistance, alcohol resistance, etc. Therefore, even when the gold and silver threads of the present invention are knitted together with undyed polyester fibers and then dyed with disperse dyes, the polyester fibers are dyed, but the gold and silver threads are not contaminated at all, and the gold and silver threads are not contaminated. The effect is that a woven or knitted fabric can be obtained that retains its original excellent metallic luster. Therefore, it is extremely convenient because conventionally yarn-dyed fibers and gold and silver threads had to be woven and knitted, but can be piece-dyed after weaving and knitting. In addition, the surface does not get dirty even during various processing steps during weaving and knitting, such as during weight loss treatment with caustic soda, etc., and furthermore, the surface hardness is high, so it is smooth and easy to weave and knit. In addition, even in the case of gold and silver threads containing a metal vapor deposited layer of silver or aluminum, the surface is protected by a transparent inorganic metal compound vapor deposited layer that is non-porous and has excellent chemical resistance, stain resistance, and abrasion resistance. Therefore, the gold and silver threads of the present invention and woven and knitted fabrics using the same are not affected by hydrogen sulfide gas, water vapor, oxygen, or sulfur compounds in the atmosphere during storage or use, so they can last for a long time. It also has the effect of preserving the original metallic luster of gold and silver thread. Next, the gold and silver thread of the present invention will be explained using the drawings. FIG. 1 is a sectional view showing one embodiment of the gold and silver thread of the present invention, in which 1 is a base film, on one side of which a metal vapor deposited layer 2 is provided, two such metal vapor deposited films are formed into a base film 1. on the inside with an adhesive layer 3 interposed therebetween, and a transparent inorganic metal compound vapor deposited layer 4 on the metal vapor deposited layer 2.
is formed. FIG. 2 is a sectional view showing another embodiment of the gold and silver thread of the present invention.
is interposed therebetween, and an intermediate coating layer 6 is further interposed between the metal vapor deposited layer 2 and the transparent inorganic metal compound vapor deposited layer 4. FIG. 3 is a sectional view showing still another embodiment of the gold and silver thread of the present invention, in which a metal vapor deposited layer 2 is provided on both sides of the base film 1, and a transparent inorganic metal compound vapor deposited layer 4 is provided on the metal vapor deposited layer 2. It is provided. The present invention improves stain resistance against dyeing of gold and silver threads using conventional base films such as polyester films, and also improves sulfidation resistance, heat resistance,
Physical and chemical properties such as light resistance, chemical resistance, sweat resistance, solvent resistance, abrasion resistance, and alcohol resistance have also been improved, making it suitable for long-term storage of gold and silver threads and woven and knitted fabrics made with them. The goal is to improve the original metallic luster of the gold and silver threads so that they can be maintained during use. Therefore, a polyester film such as polyethylene terephthalate is usually suitably used as the base film 1, but other dyes may be used. The present invention is also applicable to cases where a film that is easily dyed, such as a film made of cellulose acetate, polycarbonate, or polyamide, or a film that is difficult to be dyed, such as a film made of polypropylene, polyethylene, or fluororesin, is used as the base film 1. It is. Although the base film 1 may be an unstretched film, a uniaxially or biaxially stretched film is usually preferably used, and its thickness is usually about 2 to 50 μm, preferably about 6 to 25 μm. As the metal vapor deposition layer 2, for example, silver, gold, copper,
Examples include single metals such as nickel, chromium, platinum, palladium, indium, aluminum, zinc, and tin, and vapor-deposited layers of alloys or mixtures of two or more of these metals, and there are no restrictions on the method of forming them.
Any conventional method such as a vacuum evaporation method, a sputtering method, or an ion plating method can be employed. As the vapor-deposited metal, silver and gold are preferably used from the viewpoint of their nobility and excellent color, and aluminum is preferably used from the viewpoint of economy and brightness. The thickness of the metal vapor deposited layer is usually 30 to 200 mμ, preferably 0 to 200 mμ.
It is about 100mμ. The undercoat layer 5 is provided when the adhesion between the base film 1 and the metal vapor deposited layer 2 is poor. Undercoat layer 5
Examples of resin paints for use include those based on melamine resins, acrylic resins, and epoxy resins, and the thickness thereof is usually about 0.5 to 1.5 μm. In the present invention, a transparent inorganic metal compound vapor deposited layer 4 is provided on the metal vapor deposited layer 2 of the base film 1. Here, as the transparent inorganic metal compound vapor deposition layer 4,
For example, aluminum, barium, calcium,
Cerium, chromium, indium, lead, lithium,
potassium, magnesium, sodium, silicon,
tin, titanium, zinc, zirconium, molybdenum,
tantalum, tungsten, iron, strontium,
Oxides (excluding those consisting only of silicon oxide), fluorides, chlorides, sulfides, carbonates, nitrates, sulfates, nitrides, carbides, etc. of metals such as vanadium, thorium, antimony, platinum, bismuth, etc. The formation method is not limited in any way, and may be a vacuum deposition method, a reactive deposition method, a sputtering method, a reactive sputtering method, an ion plating method, a reactive ion plating method, etc. Any conventional method for forming a thin film of an inorganic metal compound may be employed. As the transparent inorganic metal compound, aluminum oxide, aluminum nitride, etc. or a mixture mainly composed of these are preferable from the viewpoint of their excellent properties such as transparency, chemical resistance, stain resistance, and abrasion resistance. used. The thickness of the transparent inorganic metal compound vapor deposited layer 4 is usually 5~
500 mμ, preferably selected from the range of 20 to 100 mμ. If the thickness of the transparent inorganic metal compound vapor-deposited layer is less than 5 mm, it will have poor stain resistance, sulfide resistance, heat resistance, light resistance, chemical resistance, sweat resistance, solvent resistance, abrasion resistance, alcohol resistance, etc. It is undesirable because it has poor physical and chemical properties, causing discoloration of the metal vapor deposited layer, and decreased gloss. On the other hand, although it may exceed 500 mμ, it is not preferable for general use from the economic point of view. The transparent inorganic metal compound vapor deposited layer may be colored as long as it is transparent or translucent, and colorants such as manganese compounds (purple), cobalt compounds (purple), copper (blue, red),
It may be colored with gold (red), silver (various heterogeneous colors), sulfur (yellow, brown), carbon (yellow, brown), uranium compounds (green-yellow), etc. The intermediate coating layer 6 is provided when the adhesion between the metal vapor deposited layer 2 and the transparent inorganic metal compound vapor deposited layer 4 is poor, or when metallic luster of various colors not limited to the metallic luster inherent to the vapor deposited metal is desired. , such as urea resin, melamine resin, epoxy resin,
0.5 ~ using resin paint such as urethane resin type
It is formed to a thickness of about 1.5μ. For the latter purpose, it may be appropriately colored with a coloring agent such as a dye or a pigment. The adhesive layer 3 for laminating two metallized films is not particularly limited as long as it has good water resistance and chemical resistance; for example, epoxy-isocyanate adhesives, polyester-isocyanate adhesives, etc. can be used. The thickness is usually about 1 to 2 μm. The gold and silver thread of the present invention comprises (A) a base film 1 with a metal vapor deposited layer 2 formed on one side and a transparent inorganic metal compound vapor deposited layer 4 formed on that surface;
(B) laminated with base film 1 on the inside through adhesive layer 3, or (B) base film 1
A film with a metal vapor deposited layer 2 formed on one side of the
(C) The base film 1 is laminated with the adhesive layer 3 interposed therebetween, and then the transparent inorganic metal compound vapor deposited layer 4 is formed on the exposed surface of the metal vapor deposited layer 2. It can be obtained by laminating a metal vapor-deposited layer 2 and a transparent inorganic metal compound vapor-deposited layer 4 on both sides of the transparent inorganic metal compound layer 1 in this order. The thus obtained laminate is slit into a width of about 0.15 to 3 mm using a micro slitter or the like. This slit yarn may be used as it is, but it may also be used as a twisted yarn by round twisting the core yarn, by twisting the yarn into a feather, or by cross-twisting other yarns using the slit yarn as the core.
It can also be twisted roundly around a paper or wire core and integrated with adhesive to make decorative thread for handicrafts, mizuhiki crafts, etc. The gold and silver thread of the present invention has excellent properties such as stain resistance, sulfurization resistance, heat resistance, light resistance, chemical resistance, sweat resistance, solvent resistance, abrasion resistance, and alcohol resistance. The gold and silver thread of the invention and woven and knitted fabrics using the same are exposed to hydrogen sulfide gas, hydrogen sulfide gas, etc. in the atmosphere during storage and use.
Water vapor, oxygen or sulfur compounds, sweat from hands,
The effect is that the original metallic luster of the gold and silver thread is maintained for a long period of time without being affected by friction, washing, etc. In addition, it is suitably used for weaving and knitting together with fibers that can be dyed with disperse dyes, such as polyester fibers, polyester ether fibers, polyamide fibers, acrylic fibers, cellulose acetate fibers, regenerated cellulose fibers, and cotton. Even when such a woven or knitted fabric is dyed with a disperse dye, the gold and silver threads are not contaminated at all, and the original metallic luster of the gold and silver threads is maintained. Furthermore, even when polyester woven or knitted materials are subjected to dioseting processing or silk woven or knitted materials are subjected to scouring processing, the original metallic luster of the gold and silver threads is maintained as is. Next, the gold and silver threads of the present invention will be explained with reference to Examples. Example 1 One side of a biaxially stretched polyethylene terephthalate film with a thickness of 12μ was coated with a special modified melamine resin paint [Yuban #80S manufactured by Mitsui Toatsu Chemical Co., Ltd. (solid content concentration
50% (by weight, the same applies hereinafter)) and 90% xylene-toluene mixed solvent ((mixing ratio 1:1 (weight ratio, the same applies hereinafter))] and dries to a thickness of 1 μm. An 80 mμ thick silver vapor deposited layer was formed thereon using a vacuum evaporation method, and a colorless and transparent aluminum oxide vapor deposited layer 100 μm thick was further formed thereon using a vacuum evaporation method. An adhesive solution [Takerakku A-310 manufactured by Takeda Pharmaceutical Co., Ltd.] was applied to the other side of the silver vapor-deposited film thus obtained.
(solid content concentration 50%) and Takeda Pharmaceutical Co., Ltd.'s Takerakku A-3 (solid content concentration 75%) mixture (mixture ratio
12:1) and 70% methyl ethyl ketone-ethyl acetate mixed solvent (mixing ratio 1:1)] was initially dried at 130°C to form an adhesive layer with a thickness of 1.5μ. The other surface of the silver vapor-deposited film (polyethylene terephthalate film) was placed on the surface of the adhesive layer with the other surface (polyethylene terephthalate film) facing inside, and thermocompression bonded at 150.degree. The thus obtained laminate was slit to a width of 0.43 mm using a micro slitter to obtain silver thread. This silver thread is woven together with polyester fibers, and the resulting fabric is reduced in weight by boiling in an aqueous solution containing 40 g of sodium hydroxide for 60 minutes.
%) and used as dioset, and then dyed with Kayalon Polyester Black BR-SF (black disperse dye manufactured by Nippon Kayaku Co., Ltd.) 5% owf by high pressure method (130°C x 60 minutes). The polyester fiber part of the resulting fabric was dyed black, but the silver thread part was completely uncontaminated and exhibited its original silver luster. Comparative Example 1 Instead of a colorless and transparent aluminum oxide vapor deposited layer with a thickness of 100 mμ, an n-butanol modified melamine resin paint [Yuban #20S (manufactured by Mitsui Toatsu Chemical Co., Ltd.) (solid content concentration 50) was applied on top of the silver vapor deposited layer. %) and 88% toluene-xylene-n-butanol mixed solvent (mixing ratio 1:1:1)] was applied and dried to form a top coat resin layer with a thickness of 1.2μ.
A silver thread was prepared in the same manner as in Example 1, and a woven fabric was prepared and dyed using the silver thread in the same manner as in Example 1. The polyester fiber part of the resulting fabric was dyed black, but the silver thread part had dull silver luster and was stained black. The silver threads obtained in Example 1 and Comparative Example 1 were tested under the following conditions, and changes in the gloss and color of the samples after the test were observed. The results are shown in Table 1. Gloss and color changes were evaluated using the following 5-level evaluation. Evaluation value 5 Very good 4 Good 3 Fairly good 2 Fairly poor 1 Poor Abrasion resistance Gakushin friction tester 20,000 times hot water resistance Immersed in pure water at 45°C for 240 hours Moisture resistance 70°C, RH95% 24 hour light resistance Aedometer 300 hour solvent resistance 24 hour immersion in petroleum benzine at 20°C Alkali resistance 10 hour immersion in 5% NaOH aqueous solution at 20°C Acid resistance 10 hour immersion in 10% _H2SO4 aqueous solution at 20 _° C Heat resistance 200 ℃, 1 minute sweat resistance Compliant with JIS L 0848A-1 method Alcohol resistance 20℃, 80% ethanol aqueous solution Sulfide resistance Left in hydrogen sulfide gas for 90 minutes [Table]

[Brief explanation of the drawing]

Fig. 1 is a sectional view showing one embodiment of the gold and silver thread of the present invention, Fig. 2 is a sectional view showing another embodiment, and Fig. 3 is a sectional view showing another embodiment.
The figure is a sectional view showing still another embodiment. Main symbols in the drawing: 1: base film, 2: metal vapor deposition layer, 3: adhesive layer, 4: transparent inorganic metal compound vapor deposition layer.

Claims (1)

[Claims] 1. Two base films each having a metal vapor deposited layer on one side are laminated with the metal vapor deposited layer on the outside via an adhesive layer, or two base films each having a metal vapor deposited layer on both sides of the base film are laminated with an adhesive layer interposed therebetween. Gold and silver thread, characterized in that it is a slit thread of a laminate having a structure in which a transparent inorganic metal compound vapor deposited layer (excluding one consisting only of silicon oxide) is formed on a metal vapor deposited layer. . 2. The gold and silver thread according to claim 1, wherein the base film is a polyester film. 3. The gold and silver thread according to claim 1 or 2, wherein an undercoat layer is interposed between the base film and the metal vapor deposited layer. 4. Claims 1 and 2, wherein the transparent inorganic metal compound vapor deposition layer is an aluminum oxide vapor deposition layer.
The gold and silver thread described in Items 1 and 3.