JP3969962B2 - Metal-deposited laminated film and slit yarn - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal-deposited laminated film that can be suitably used for a metallic glossy slit yarn (gold and silver yarn) and the like, and a metallic glossy slit yarn obtained by slitting the film. More specifically, when used as a gold-silver thread, that is, a metallic glossy slit thread, the metal thin film layer portion does not crack in high-speed, high-stress twisted yarns, knitting, etc. A metal-deposited laminated film having a metal thin film layer detachment of 20% or less in area and slitting it under conditions corresponding to scouring conditions such as polyester in a treatment of PH10 at 100 ° C. for 2 hours. It is related with the metallic glossy slit thread (gold-silver thread) obtained by this.
[0002]
[Prior art]
Gold and silver threads are widely used, in which a laminated film is thinly slit, such as a film such as a polyester film on which a metal such as aluminum is evaporated and a colored or transparent uncolored protective layer mainly composed of a resin is provided thereon. ing.
[0003]
[Problems to be solved by the invention]
In conventional gold and silver yarns, metal thin film layers, metal slits caused by cracks in the metal thin film layers due to chemicals, heat, friction, etc. in slits of films provided with resin layers, warping of slit yarns, twisting yarns, weaving, dyeing, finishing, etc. It suffered from the loss of glitter and the damage of the colored resin layer provided on the metal thin film layer for specific coloring of the metal thin film layer, resulting in damages such as loss of value as a gold-silver thread. There has been a demand for gold and silver yarns that are excellent in retainability against various chemicals, heat, friction, and the like in each step because of loss of colored colors and metallic luster.
The present invention overcomes the above-mentioned conventional drawbacks, and makes it possible to slit a metal-deposited laminated film having excellent retention of various colors, loss of metallic luster and various stretches, chemicals, heat, friction, etc. in each process. The object is to provide a metallic glossy slit yarn (gold and silver yarn) obtained in the above.
[0004]
[Means for Solving the Problems]
That is, the present invention is a metal vapor-deposited laminated film in which at least a metal vapor-deposited thin film layer and a resin layer are provided in this order on at least one side of the film, and the gloss reduction rate when the metal vapor-deposited laminated film is stretched 30% is 20 %, The reflectivity maintenance rate is 80% or more, and the metal vapor deposition thin film layer is detached at an area of 20% or less in a treatment at a pH of 10 at 100 ° C. for 2 hours. And a metal glossy slit formed by slitting the metal vapor-deposited laminated film, wherein at least the metal vapor-deposited thin film layer and the resin layer are provided in this order on both sides of the film. It is a thread.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, in the metal glossy slit yarn formed by slitting the metal vapor deposition laminated film in which at least the metal vapor deposition layer and the resin layer are provided in this order on one or both surfaces of the film, at least the metal vapor deposition layer on both surfaces of the film, A metallic glossy slit thread formed by slitting a metal vapor-deposited laminated film provided with resin layers in this order is a more preferred embodiment. That is, the slit yarn from the metal vapor-deposited laminated film provided with the metal vapor-deposited thin film and the resin layer on both sides of the film has an unmistakable metallic luster on both sides, and a thin laminated film is obtained as a whole. There is no difference between the front and back, and it is easy to obtain a thin and flexible slit thread. In the present invention, if necessary, an anchor layer may be provided between the film and the metal vapor-deposited thin film layer, and these anchor layer resins are also particularly limited as long as they do not depart from the gist of the present invention. is not.
[0006]
The film used in the present invention is not particularly limited, but polyethylene terephthalate and copolymers thereof, polytrimethylene terephthalate and copolymers thereof, films from polyester such as polyethylene naphthalate and copolymers thereof, nylon 6, Examples thereof include a polyamide film such as nylon 66 and a transparent or translucent film such as a polyolefin film. Among them, a polyethylene terephthalate film can be preferably used.
As the film used in the present invention, a non-stretched film, a uniaxially stretched film, a biaxially stretched film, a sequential biaxially stretched film, or the like is appropriately used.
The thickness of these films is preferably about 4 to 50 μm, more preferably about 6 to 25 μm. Most preferred is a biaxially stretched polyethylene terephthalate film having a thickness of 6 to 12 μm.
[0007]
When the thickness of the film is less than 4 μm, it is difficult to form an industrial wide and long film, the yield is poor, the production cost is high, and the process for providing the metal vapor deposition thin film layer is performed. Damage, generation of wrinkles, etc. occur and are often undesirable. On the other hand, when the film with a thickness exceeding 50 μm loses the flexibility of the gold-silver thread and is mixed with other fibers to produce a product, the hardness of the metallic glossy slit thread in the fiber product comes to the front, and accordingly, the softness inherent to other fibers becomes softer. Since a supple texture is impaired, it is not preferable. The metallic glossy slit yarn used in the present invention determines the weaving property, knitting property, and texture because the mechanical properties of the film influence the mechanical properties of the slit yarn obtained almost as it is. Considering this, it is appropriately selected from the above range.
The film may be formed by adding a plastic anti-aging agent such as an ultraviolet absorber or an antioxidant, an antistatic agent, or a slipping agent to the extent that the gist of the present invention is not impaired. can do.
[0008]
In the present invention, if necessary, an anchor layer (undercoat layer) may be used. The anchor layer coating material may be an acrylic resin, a nitrocellulose resin, a urethane resin, a melamine resin, an epoxy resin, or the like. Apply an organic solvent solution of resin, aqueous solution, etc. to a uniform thickness by a normal coating method such as gravure coating method, spray coating method, etc., and dry (such as thermosetting resin, electron beam curable resin, UV curable resin, etc.) In some cases, the coating is formed by curing).
The thickness of the undercoat layer is usually in the range of 0.005 to 2 μm, preferably in the range of 0.01 to 1 μm. If the thickness of the resin undercoat layer is less than the above range, it hardly contributes to the improvement of post-dyeing suitability, adhesion to the metal vapor deposition layer, etc., and it is not preferable because it is not meaningful. On the other hand, if the above range is exceeded, the metallic glossy slit yarn becomes rigid as a whole, which is not preferable.
[0009]
The resin layer (top layer) provided on the metal vapor-deposited thin film layer in the present invention is particularly a resin layer in which the gloss reduction rate of the metal vapor-deposited thin film layer portion at the time of 30% elongation of the present invention is 20% or less. Although not limited, Preferably, polyurethane resins such as acrylic polyol polyurethane, polyester polyurethane, and polyether polyurethane can be preferably used. Among them, an acrylic polyol polyurethane is preferable, and among them, an acrylic polyol having a number average molecular weight of 10,000 or more and OH of 25 or less, preferably a Tg of 80 ° C. or more, and an isocyanate for forming a urethane bond, Preferably, it is an aliphatic diisocyanate or a cyclized product of isocyanurate from them, and the resin layer (top layer) has adhesiveness with a metal-deposited thin film layer at 30% elongation, cracks, pinholes and defects in the top layer itself. It is necessary to prevent the penetration of the liquid into the metal-deposited thin film layer in the treatment at PH10, 100 ° C. for 2 hours. A resin other than the polyurethane resin may be added to these resin layers as long as they do not impair the gist of the present invention, and other heat stabilizers, ultraviolet absorbers, fillers, and the like may be added. In the present invention, the resin layer may contain a pigment as a colorant. The pigment may be either an organic pigment or an inorganic pigment, and is not particularly limited, but an organic pigment can be preferably used from the viewpoint of dispersibility and translucency. As these pigments, for example, organic pigments and inorganic pigments described in, for example, a well-known color material engineering handbook (1989, Asakura Shoten) can be used, and they are appropriately selected and used in terms of color tone, cost, dyeing resistance and the like. The content of the pigment in the resin layer is not particularly limited, but is preferably in the range of 0.1 to 10% by weight. The thickness of this resin layer should just be the range of 0.5-6 micrometers, More preferably, it is 1-5 micrometers , and when less than 0.5 micrometer , it is inadequate also in coloring, PH10, 100 degreeC, 2 The penetration of the liquid into the metal vapor-deposited thin film layer during the time treatment cannot be prevented, and when it exceeds 6 μm, not only the above-mentioned effect is not improved, but also the flexibility of the obtained metallic glossy slit yarn is impaired. It is not economically advantageous. The method for forming these resin layers is not particularly limited, and may be appropriately selected from roll coating methods, bar coating methods, gravure coating methods, reverse coating methods and the like.
[0010]
The metal vapor-deposited thin film layer used in the present invention imparts a strong metallic luster to the metallic glossy slit yarn of the present invention, and is provided on one side or both sides of the film. For the metal thin film layer, for example, gold, silver, aluminum, chromium, nickel, copper, palladium, indium, lead, platinum, zinc, tin and the like are usually used. Among these, aluminum and tin are particularly preferably used when importance is attached to the cost and more glitter is required.
The thickness of the metal vapor-deposited thin film layer is preferably 10 nm to 100 nm, more preferably 20 nm to 80 nm. The formation of the metal thin film layer is not particularly limited as the method, and can be appropriately selected and used from a vacuum deposition method, a sputtering method, an ion plating method and the like.
[0011]
The thickness of the metal vapor-deposited thin film layer is in the range of about 10 to 100 nm, and the range of 20 to 80 nm is particularly preferable. If the thickness of the metal vapor-deposited thin film layer obtained by vapor deposition is less than the above range, the metallic luster is poor, which is not preferable. On the other hand, even if the above range is exceeded, the brightness as a metallic glossy slit yarn does not increase, but cracks tend to occur, and the whole becomes stiff and lacks in texture, which is not preferable.
The method for forming the metal vapor-deposited thin film layer is not particularly limited. For example, a conventional vapor deposition method such as a resistance heating method, a high-frequency induction heating method, an electron beam heating method, or an ion plate using the metal, alloy, or metal compound described above. It can be formed by a deposited film forming method such as a coating method, a sputtering method, or an ion beam method.
[0012]
The metallic glossy slit yarn in the present invention is preferably a metallic glossy slit yarn formed by slitting a metal vapor-deposited laminated film in which at least a metal thin film layer and a resin layer are provided in this order on both sides of the film, The vapor-deposited laminated film has a gloss reduction rate of 20% or less and a reflectivity maintenance rate of 70% or more when stretched by 30%. Furthermore, when the film is deposited at a pH of 10 and 100 ° C. for 2 hours, the metal vapor-deposited thin film layer is detached. Is less than 20%, more preferably at 130 ° C. for 60 minutes under high pressure dyeing conditions for polyester fibers, and the desorption of the metal-deposited thin film layer is 20% or less in area, and this metal-deposited laminated film is slit It is a metallic luster slit yarn obtained by doing. The metallic glossy slit yarn is obtained by microslitting the laminated film to a width of usually about 0.15 to 2 mm, and inherits the performance of the metal-deposited laminated film.
[0013]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
【Example】
** Example 1
Aluminum is vapor-deposited on both sides of a polyethylene terephthalate film having a thickness of 12 μm, and acrylic polyol (number average molecular weight 10,000, OH value 20) 100 parts (weight, hereinafter the same), aliphatic diisocyanate on both aluminum surfaces. A coating solution consisting of 30 parts of a system curing agent (isocyanurate cyclized product of hexane diisocyanate) and 18.2 parts of methyl ethyl ketone was applied, followed by drying and curing at 180 ° C. for 30 seconds and further at 90 ° C. for 12 hours, and a dry film thickness of 2 μm. A resin layer was formed. The obtained metal-deposited laminated film and it was slit to a width of 0.3 mm to obtain gold and silver thread samples, and various evaluations were made.
[0014]
** Comparative example 1
Aluminum is vapor-deposited on both sides of a 12 μm thick polyethylene terephthalate film, and 100 parts of acrylic polyol (number average molecular weight 7000, OH value 30), 10 parts of toluene diisocyanate curing agent, methyl ethyl ketone are formed on both aluminum surfaces. A coating solution consisting of 18.2 parts was applied and subjected to a drying and curing treatment at 180 ° C. for 30 seconds and further at 90 ° C. for 12 hours to form a resin layer having a dry film thickness of 2 μm. The obtained metal-deposited laminated film and it was slit to a width of 0.3 mm to obtain gold and silver thread samples, and various evaluations were made.
[0015]
** Comparative example 2
Aluminum is vapor-deposited on both sides of a 12 μm thick polyethylene terephthalate film at a thickness of 600 mm, and a coating solution consisting of 27 parts of melamine resin and 18.2 parts of methyl ethyl ketone is applied to both aluminum surfaces, and the temperature is 180 ° C. for 30 seconds. Drying and curing treatment was performed to form a resin layer having a dry film thickness of 2 μm. The obtained metal-deposited laminated film and it was slit to a width of 0.3 mm to obtain gold and silver thread samples, and various evaluations were made.
[0016]
Samples in Example 1 and Comparative Examples 1 and 2 (in the case of a film, n is an average of 3 × 15 cm in a state of being cut to a size of 3 × 15 cm, and in the case of slit yarn, the sample is cut to a length of 10 cm) The following evaluation was carried out on the average of 10 of which were the same.
▲ 1 ▼ 《Dyeing evaluation》
** Dyeing conditions (E) (polyester dyed)
Amirazine D: 0.1 g / l
Acetic acid: 1.0 g / l
Surfactant (Monogen 170T): 0.2 g / l
Disperse dye for polyester (blue): 0.01 g / l
130 ° C x 60 minutes, bath ratio 1:30
Dye each sample under the above staining conditions,
** Reduction treatment conditions Hydrosulfite: 2.0 g / l
Soda ash: 2.0 g / l
Amylazine D: 1.0 g / l
80 ° C. × 20 minutes, bath ratio 1:50
In comparison with the appearance of the dye-deposited thin film layer before and after the dye-reduced treatment, the metal-deposited thin-film layer area S ₀ before the treatment is defined as 100, and the metal-deposited thin-film layer after the treatment is reduced. The area S ₁ was measured, and the residual rate S _S (%) was calculated and evaluated according to the following formula.
S _S = ((S ₀ −S ₁ ) / S ₀ ) × 100
[0017]
(2) << Extension evaluation >>
The obtained sample was stretched at a speed of 300 mm / min using a fiber strength measuring machine, and the glossiness K (60 °) and reflectance H (550 nm) of the sample when stretched 30% were measured. The gloss reduction rate ΔK (%) and reflectance maintenance rate σH (%) were calculated from the following formulas and evaluated from the values at K ₀ , H ₀ before stretching and K ₃₀ , H ₃₀ after stretching.
ΔK = ((K ₀ −K ₃₀ ) / K ₀ ) × 100
σH = (H ₃₀ / H ₀ ) × 100
[0018]
(3) << Evaluation of anti-PH10 solution treatment >>
The obtained sample, PH10,100 ℃, 2 hours of processing, in the appearance of the sample after processing, by comparing the before and after by the processing of the metal deposition film layer, a metal deposition film layer area Z ₀ before treatment 100, the treated metal vapor-deposited thin film layer area Z ₁ was measured, and the desorption area ratio Z _P (%) was calculated from the following formula and evaluated.
Z _P = ((Z ₀ −Z ₁ ) / Z ₀ ) × 100
The treatment liquid used was an alkaline substance having surface activity, for example, a soap obtained by dissolving a commercially available soap, which is sodium fatty acid, in water, PH10, and treated at a bath ratio of 1:50 at 100 ° C. for 2 hours.
[0019]
As a result of the evaluation, the gloss reduction rate ΔK (%) of the film of Example 1 is 17%, the reflectance maintenance factor σH (%) is 96%, the residual rate S _S (%) is 99%, and desorption The area ratio Z _P (%) was almost 0%.
The residual rate S _S (%) of the slit yarn of Example 1 was 99%, and the detached area rate Z _P (%) was almost 0%.
* The gloss reduction rate ΔK (%) of the film of Comparative Example 1 is 25%, the reflectance maintenance rate σH (%) is 75%, the residual rate S _S (%) is 70%, and the desorption area rate Z _P (%) was 30%.
The residual rate S _S (%) of the slit yarn of Comparative Example 1 was 65%, and the detached area rate Z _P (%) was 35%.
* The gloss reduction rate ΔK (%) of the film of Comparative Example 2 is 30%, the reflectance maintenance rate σH (%) is 75%, the residual rate S _S (%) is 65%, and the desorption area rate Z _P (%) was 35%.
The residual rate S _S (%) of the slit yarn of Comparative Example 2 was 65%, and the detached area rate Z _P (%) was 35%.
[0020]
【The invention's effect】
The metal-deposited laminated film according to the present invention and the metal glossy slit yarn obtained by slitting the metal-deposited film do not crack the metal-deposited thin film layer due to friction, stretching, etc. in various processes, and dye under more severe dyeing conditions. In addition, the metallic luster and coloring previously imparted to the metallic glossy slit yarn can be maintained, and even in the dyeing of products knitted with other fibers, it is possible to maintain the glitter and color of the original metallic glossy slit yarn, A decorative effect can be imparted to such products relatively easily, and the effect is great.
Furthermore, the metallic glossy slit yarn according to the present invention and the twisted yarn or spun yarn using the metallic glossy slit yarn and the fiber product using the same can be easily dyed by the dyeing method for each fiber, and the metallic glossy slit yarn is originally colored. Has the effect of being easy to maintain.

Claims (1)

  On one or both sides of the film,
  At least a metal-deposited thin film layer, a resin layer, and a metal-deposited laminate film provided in this order,
  When the metal-deposited laminated film has a 30% elongation, the gloss reduction rate is 20% or less, the reflectance maintenance factor is 80%, and the treatment of Ph10 at 100 ° C. for 2 hours removes the metal-deposited thin film layer. Separation is 20% or less in area, slitting a metal-deposited laminated film,
  Characteristic, metal glossy slit yarn.