JP5496120B2 - Silver yarn and twisted yarn, woven fabric and knitted fabric using silver yarn - Google Patents

Description

  The present invention relates to a slit silver yarn that can be post-dyed at normal pressure, and a twisted yarn, a woven fabric, and a knitted fabric using the silver yarn.

  A silver thread obtained by slitting a laminated film in which a metal thin film is formed on a resin film substrate has been known for a long time, and Ag, Al, and Sn are used as the metal thin film. Among them, the one using Ag is called a pure silver thread and has a bright reflection color tone, whiteness, and excellent alkali resistance.

  When Ag is used as the metal, Ag should not be corroded by moisture from the moisture-absorbing resin film, and it is necessary to use a resin that can be baked at high temperatures for the anchor coat (underlayer) or top coat (protective layer). There is. Therefore, a polyester film having a low hygroscopic property and a high heat resistance is exclusively used as the resin film.

  For example, in Patent Documents 1 to 3, various types of slit silver yarn using Ag are described, and the base material is a polyester film.

  However, the polyester film is hard and lacks in texture, and cannot be sufficiently dyed with acid dyes or direct dyes. Therefore, when importance is attached to more supple texture and post-dyeing, silver yarn using nylon film and Al, Sn or the like as a metal is still used.

In Patent Document 4, two laminated films in which an anchor coat, a metal vapor deposition layer such as Ag, and a top coat layer are provided on one side of a polyester film and a polyamide layer is applied and dried on the other side are bonded to each other. A georgette silver thread is described. While using a polyester film substrate and Ag, by providing a polyamide resin layer as the outermost layer, the texture of the georgette is improved and post-dyeing under normal pressure is possible.
However, the silver thread of Patent Document 4 has a polyester film thickness of 12 μm, whereas the polyamide layer has a thickness of only about 1.5 μm, and the layer dyed by acid dyeing is too thin and deep. A certain color cannot be produced. In addition, since the polyester film is thicker than the polyamide layer, it is inferior to the touch and texture. Therefore, a georgette process is required to improve the texture.

Japanese Patent Laid-Open No. 08-81843 Japanese Patent Laid-Open No. 11-269732 JP 2005-350812 A Japanese Patent Laid-Open No. 62-276042

  The present invention has been made in consideration of such points, and an object of the present invention is to provide a silver thread that is soft in texture and can be post-dyed at normal pressure while having a bright reflective color tone and an excellent appearance. .

The silver thread according to the present invention is a silver thread obtained by slitting a laminated film into a narrow width, and the laminated film has at least five layers of a polyamide layer, a polyester layer, a metal thin film layer, a top coat layer, and an adhesive layer in this order, The metal thin film layer is made of Ag or Al, and the polyamide layer and the polyester layer are partly or entirely formed of a multilayer resin film integrally formed by coextrusion , and the thickness of the polyamide layer is 3 to 3 15 μm, the thickness of the polyester layer is 1 to 5 μm, the reflection color of the obtained laminated film is L ^* value of 94.51 or more when the metal thin film layer is Ag , the metal thin film layer In the case where Al is Al, the L ^* value is 91.03 or more .
By adopting such a structure, a soft texture is obtained by the polyamide layer, and it is possible to perform after-dyeing at normal pressure, the reflection color tone is bright by the polyester layer, and in the case of an achromatic color, white is outstanding and has an excellent appearance. Can be obtained. In addition, the polyamide layer and the polyester layer form a part or the whole of the multilayer resin film by coextrusion, whereby a silver thread with higher gloss can be obtained. Further, by setting the thicknesses of the two layers within this range, the reflection color tone and the texture can be achieved at a higher level. And it can be set as a silver thread with a more supple texture, without performing georgette processing.

Preferably, the metal thin film layer is made of Ag.
By using a pure silver thread using Ag, the reflection color tone can be brightened.

Preferably, the laminated film further includes an anchor coat layer between the polyester layer and the metal thin film layer.
Thereby, the adhesiveness of a polyester layer and a metal thin film layer can be improved, and thereby durability of a silver thread can be improved. Further, the reflection color tone can be brightened.

Preferably, the laminated structure of the laminated film is symmetric about the adhesive layer.
As a result, the same color, gloss, and dyeability can be obtained from either side of the silver thread, which is advantageous when the silver thread is twisted in use. However, when using only one side like the case of using a round twisted yarn, it can be bonded to paper.

The twisted yarn according to the present invention uses any of the above-described slit silver yarns.
The woven fabric according to the present invention uses the slit silver yarn according to the present invention and / or the twisted yarn according to the present invention.
The knitted fabric according to the present invention uses the slit silver yarn according to the present invention and / or the twisted yarn according to the present invention.

  As described above, according to the present invention, it is possible to obtain a silver yarn having an excellent appearance with a bright reflected color tone and a soft texture and capable of being post-dyed at normal pressure.

It is a figure which shows the laminated structure of the silver thread which concerns on one Embodiment of this invention.

  The silver yarn according to the present invention is produced by slitting a laminated film into a narrow width. Then, about one Embodiment of the silver thread which concerns on this invention, the laminated structure is demonstrated based on figures.

FIG. 1 shows the laminated structure of this embodiment.
In order from the bottom of FIG. 1, polyamide layer 1, polyester layer 2, anchor coat layer 3, metal thin film layer 4, top coat layer 5, adhesive layer 6, top coat layer 15, metal thin film layer 14, anchor coat layer 13, polyester layer 12 and a polyamide layer 11.
The entire laminated structure is symmetrical on the upper side and the lower side with the adhesive layer 6 as the center. The whole of FIG. 1 is formed by adhering two laminated films composed of a polyamide layer 1 to a top coat layer 5 and bonding the top coat layers together.

The polyamide layer 1 contains a polyamide resin as a main component. As the polyamide resin, various polyamides such as nylon 6, nylon 6, 6, and nylon 12, and copolymers thereof can be used alone or in combination. Preferably, a material mainly composed of nylon 6 can be used. Further, it may contain a resin other than polyamide and various inorganic / organic additives and other components for improving characteristics.
Further, preferably, the polyamide layer 1 is obtained by simultaneous biaxial stretching or sequential biaxial stretching. This is because in the case of non-stretching or uniaxial stretching, when the film is micro-slit to form a yarn, the yarn stretches with a weak force, the breaking strength is weak, and the yarn shrinks or deforms even on a heat resistant surface.
The thickness of the polyamide layer 1 is preferably 3 to 25 μm. When the thickness is less than 3 μm, there is no depth when the yarn is dyed by acid dyeing, and the breaking strength of the yarn is weak, making it difficult to use as a yarn. On the other hand, if it exceeds 25 μm, when the yarn is dyed by acid dyeing, the color depth does not change even if it is thicker than this, and the yarn becomes thick as a yarn. The thickness of the polyamide layer 1 is more preferably 6 to 15 μm. When the thickness is less than 6 μm, it is necessary to make the polyester resin at an equivalent thickness or more from the viewpoint of the strength of the yarn, and the texture becomes slightly worse. On the other hand, if it exceeds 15 μm, it is not optimal when considering the required thickness and cost.
The polyamide layer 1 constitutes the outermost layer of the laminated structure, that is, the surface portion of the silver thread. Thereby, a soft touch and texture are brought about and it functions as a layer to be dyed in the post-dyeing process.

The polyester layer 2 contains a polyester resin as a main component. As the polyester resin, various resins or copolymers such as polyethylene terephthalate (PET) can be used alone or in combination. Further, it may contain a resin other than polyester and various inorganic / organic additives and other components for improving characteristics.
Preferably, the polyester is biaxially stretched or biaxially stretched sequentially.
The thickness of the polyester layer 2 is preferably 1 to 9 μm. If the thickness is less than 1 μm, the moisture barrier function from nylon is inferior and the heat resistance is insufficient. On the other hand, even if it exceeds 9 μm, the moisture barrier function and heat resistance from nylon do not require any more thickness. The thickness of the polyester layer 2 is more preferably 2 to 5 μm. If the thickness is less than 2 μm, the heat resistance is insufficient, and if it exceeds 5 μm, it is not optimal when considering the texture and cost of the yarn.
The polyester layer 2 has a function as a barrier that blocks moisture from being released from the hygroscopic polyamide layer 1 to the metal thin film 4 side, and a function as a heat-resistant layer when processing the anchor coat layer 3 and the top coat layer 5. . That is, since the polyester layer 2 has heat resistance, it is possible to use a resin that needs to be cured at a high temperature for the anchor coat layer 3 and the top coat layer 5, and is affected by heat during the deposition of the metal thin film layer 4. As a result, the reflection color tone is bright, and in the case of an achromatic color, the whiteness is conspicuous and an excellent appearance can be given to the silver thread.

  In this embodiment, the polyamide layer 1 and the polyester layer 2 form a multilayer resin film 8 that is integrally molded. That is, the multilayer resin film 8 having the polyamide layer 1 and the polyester layer 2 is used as a base material.

By using a base material formed in advance in a multilayer film, even if the polyester layer 2 is thin, when the metal thin film layer 4 or the like is coated, the surface of the base material is not wavy and a laminated film having a bright reflection color tone can be obtained. .
On the other hand, when a polyamide layer is applied and bonded after a laminated film is produced using a polyester single layer film as a base material, the surface of the base material is undulated during coating of a metal thin film layer or the like if the polyester base material is thin. It is difficult to process and the product is finished in a dull color, and if the polyester base is thick, the entire silver thread that is the product becomes thick and hard, and a supple texture cannot be obtained.
In addition, when a silver thread is produced using a polyamide single layer film as a base material, a glossy deposited film cannot be obtained due to the moisture absorbed in the polyamide single layer film during vapor deposition. In particular, when pure silver is vapor-deposited, only a vapor-deposited film having a poor gloss due to the influence of moisture is obtained. Further, in the case of a polyamide single layer film due to radiant heat during vapor deposition or temperature applied during coating, curling, heat shrinkage, and whitening due to oligomers occur and appearance and gloss are impaired.
Therefore, the formation of a multilayer resin film in which the polyamide layer 1 and the polyester layer 2 are integrally formed in advance is an important factor in the appearance of the silver thread.

  The multilayer resin film is not limited to a polyamide / polyester two-layer structure. That is, a part of the multilayer resin film in which the polyamide layer 1 and the polyester layer 2 are integrally formed may be formed. In this case, the two surfaces of the film may be a polyamide layer and a polyester layer, or there may be a thin layer on the polyamide layer that does not interfere with post-dyeing. There may be a thin layer with no heat resistance. The polyamide layer and the polyester layer may be adjacent to each other, or some layers may be sandwiched between them. For example, a layer having good adhesion to both layers may be provided between both the polyamide and polyester layers.

  The method for forming the multilayer resin film is not particularly limited. For example, a method of simultaneously extruding a resin corresponding to a plurality of layers onto a cooling roll with a T die and stretching the extruded multilayer film in a biaxial direction with a tender is preferable. Using a film obtained by coextrusion is preferable from the viewpoint of the appearance of the silver thread to be produced because a silver thread with higher gloss is obtained, and is easy to perform post-processing when sequentially forming other layers on the polyester layer side However, it is preferable. In some cases, the interlayer strength of a plurality of films may be improved by providing an adhesive resin between the layers of the multilayer resin during extrusion and performing extrusion to interpose the adhesive layer.

The anchor coat layer 3 may be provided to improve the adhesion between the polyester layer 2 and the metal thin film layer 4.
The anchor coat layer 3 can be a single resin or a mixture of various resins such as acrylic, nitrocellulose, urethane, melamine, epoxy, and ester. In order to obtain a silver thread with high whiteness, Epoxy melamine type, acrylic melamine type or ester type are preferable.
The thickness of the anchor coat layer 3 is preferably 0.05 to 2 μm. This is because if the anchor coat layer is too thin, the effect of improving the adhesion cannot be obtained, and if it is too thick, the curing of the resin is slowed down, resulting in poor productivity and a large amount of resin, which increases the cost.
As the coating method, a known method such as gravure coating or spray coating can be used.

The metal thin film layer 4 is made of Ag or Al, most preferably Ag.
Moreover, in order to produce interference colors, a laminate of Al / SiO ₂ , Ag / SiO ₂ , Al / SiO ₂ / Al, Al / MgF ₂ / Al, Ag / SiO ₂ / Ag, Ag / MgF ₂ / Ag, etc. Vapor deposition may be performed. Since the reflection color of the interference color changes depending on the viewing angle, a unique gloss can be obtained in combination with the color shade after dyeing.
If the metal thin film layer 4 is too thin, the metallic luster is weak, which is not preferable. On the other hand, if it is too thick, cracks are likely to occur, and a burnt appearance is likely to occur. The thickness of the metal thin film layer 4 is preferably 10 to 80 nm, and more preferably 40 to 60 nm.
As a film forming method, a known method such as vacuum deposition, sputtering, or ion plating can be used.

The top coat layer 5 can be made of various resins such as acrylic, nitrocellulose, urethane, melamine, epoxy, ester, etc., but in order to obtain a silver thread with a bright reflected color, an epoxy is used. Of these, melamine-based or urethane-based ones are preferable. When Ag is used as the metal, it is preferable to use an epoxy melamine-based resin or an acrylic melamine-based resin from the viewpoint of moisture resistance and adhesion.
The thickness of the top coat layer 5 is preferably 0.5 to 2 μm. This is because if the top coat layer is too thin, the moisture resistance and adhesion are poor, and if it is too thick, the curing of the resin slows down, the productivity is poor, and a large amount of resin is required, resulting in high costs.
As the coating method, a known method such as gravure coating or spray coating can be used.
The top coat layer 5 has a function of protecting the metal thin film layer 4 from physical damage due to wear or the like, and protecting from chemical damage caused by moisture in the air and various chemicals used in subsequent processes.

The adhesive layer 6 is a layer that adheres the top coat layers 5 and 15 of the laminated film composed of the polyamide layer 1 to the top coat layer 5.
As the adhesive, various adhesives such as polyester, urethane, acrylic and ether can be used. From the viewpoint of adhesion, heat resistance and post-dyeing resistance, a two-component curable polyester adhesive is preferred.
The thickness of the adhesive layer 6 is preferably 0.5 to 3 μm. This is because if the adhesive layer is too thin, the adhesive force is poor and foil cracking may occur, and if it is too thick, the adhesive protrudes from the slit cross-section during micro slitting, causing a problem.

As described above, the description is based on FIG. 1, but the embodiment of the present invention is not limited to this.
For example, the anchor coat layer 3 is not essential, and a layer for giving color and haze may be provided in addition to the above. Further, the metal thin film layer 4 may be divided into a larger number of layers, and light interference by the laminated film may be used for color adjustment.

  In addition, since the upper and lower sides of the laminated structure in FIG. 1 are symmetrical with respect to the adhesive layer 6, the same color, gloss, and dyeability can be obtained from either side of the silver thread. However, if such symmetry is unnecessary, the resin layer only on the opposite side of the adhesive layer 6 with respect to the polyamide layer 1 to the top coat layer 5 can be used, or the polyamide layer can be omitted. Even when used as a round twisted yarn, the silver yarn is wound around the core yarn with one side facing outward, so that the target property is unnecessary, and paper or the like can be bonded to the opposite side of the adhesive layer 6.

  The twisted yarn according to the present invention is a twisted yarn using the silver yarn according to the present invention. For example, the core yarn may be round twisted using rayon yarn, cupra yarn, silk yarn, cotton yarn, suf yarn, acrylic yarn, ester yarn, nylon yarn, etc. It is possible.

The woven fabric according to the present invention uses the slit silver yarn according to the present invention and / or the twisted yarn according to the present invention. That is, generally, the twisted yarn according to the present invention using slit silver yarn is used, and the slit silver yarn carrier is woven as necessary. However, the slit silver yarn may be woven only.
The knitted fabric according to the present invention uses the slit silver yarn according to the present invention and / or the twisted yarn according to the present invention. That is, in general, the twisted yarn according to the present invention using a slit silver yarn is used, and the slit silver yarn carrier is knitted as necessary. However, the slit silver yarn may be used only for knitting.
Both the woven fabric and the knitted fabric can be manufactured by a known method, and the manufacturing method and configuration are not particularly limited.

Below, the evaluation result of several Examples and a comparative example is shown about the silver thread concerning this invention.
The composition of the samples is summarized in Table 1.

Example 1
A two-layer resin film was prepared by coextrusion and biaxial sequential stretching, consisting of a nylon layer having a thickness of 12 μm and a polyester layer having a thickness of 3 μm. On the polyester layer, an Ag thin film having a thickness of 50 nm was formed by vacuum deposition. On the Ag thin film, an epoxy melamine-based resin was applied by a gravure printing method and dried and cured at 140 ° C. for 30 seconds to provide a topcoat layer having a thickness of 1 μm. The top coat layers of the two laminated films thus produced were adhered to each other by applying a polyester adhesive with a thickness of 2 μm by a gravure printing method. The finally completed laminated film was slit into a width of 250 μm (120 cuts) to obtain a silver thread of Example 1.

(Example 2)
An acrylic melamine-based resin is applied on the polyester layer by gravure printing, and dried and cured at 180 ° C. for 30 seconds to provide an anchor coating layer having a thickness of 0.1 μm. It was manufactured by the same method as in Example 1 except that an Ag thin film was formed.

(Example 3)
A two-layer resin film was prepared by coextrusion and biaxial sequential stretching, consisting of a nylon layer having a thickness of 12 μm and a polyester layer having a thickness of 3 μm. An Al thin film having a thickness of 50 nm was formed on the polyester layer by vacuum deposition. A urethane-based resin was applied on the Al thin film by a gravure printing method, dried and cured at 120 ° C. for 30 seconds, and a topcoat layer having a thickness of 1 μm was provided. The top coat layers of the two laminated films thus produced were adhered to each other by applying a polyester adhesive with a thickness of 2 μm by a gravure printing method. The finally completed laminated film was slit into a width of 250 μm (120 cuts) to obtain a silver thread of Example 3.

(Example 4)
An ester-based resin is applied on the polyester layer by gravure printing, dried and cured at 180 ° C. for 30 seconds to provide an anchor coating layer having a thickness of 0.1 μm, and 50 nm thick Al by vacuum deposition on the anchor coating. It was manufactured by the same method as in Example 3 except that a thin film was formed.

(Comparative Example 1)
It was produced by the same method as in Example 1 except that a nylon film having a thickness of 15 μm was used instead of the two-layer resin film comprising a nylon layer and a polyester layer.

(Comparative Example 2)
It was produced by the same method as in Example 3 except that a nylon film having a thickness of 15 μm was used instead of the two-layer resin film comprising a nylon layer and a polyester layer.

(Evaluation by CIELab)
The reflection color of the silver thread was evaluated for the film-like laminate before slitting.
Using a colorimeter (Konica Minolta Co., Ltd., CM-3500d), the spectral reflectance was measured at a viewing angle of 10 degrees and a measurement diameter of 30 mm, and the reflection color for the D65 light source was determined by L ^* a ^* b of the International Lighting Commission. ^* Represented in the color system (JISZ8729).
Table 2 shows the measurement results.

When Example 1, Example 2, and Comparative Example 1 using Ag for the metal thin film layer are compared, it can be seen that the lightness L ^{* of} Examples 1 and 2 is clearly high and the reflection color tone is bright. Since both Example 1 and Example 2 are achromatic colors, white is outstanding, and it can be said that white is glossy.
Moreover, it can be seen from the comparison between Example 1 and Example 2 that the latter L ^* with the anchor coat is high.
Moreover, from the numerical value of b ^* , in Comparative Example 1, b ^* is large and yellow is strong. Ag deposition is easily affected by water, and in Comparative Example 1, it is considered that it was influenced by moisture released from the resin film substrate.

The same tendency is observed when Example 3, Example 4, and Comparative Example 2 using Al for the metal thin film layer are compared, and the lightness L ^{* of} Examples 3 and 4 is high and the whiteness is high.
The absolute value of L ^* is larger when the metal thin film is Ag. This indicates that a whiter silver thread can be produced using Ag. Moreover, the difference of L ^* of an Example and a comparative example is larger when Ag is used, and it turns out that the effect of this invention has appeared largely.

(Heat-resistant)
The film-like laminate before slitting was cut into a size of 30 mm × 200 mm, and placed in an oven at 180 ° C. for 30 seconds to evaluate heat resistance.
Table 3 shows the results. The meanings of the symbols in the evaluation column are: ○: the film after the test can be slit and used as a silver thread, x: the film after the test is slit and cannot be used as a silver thread (Table) The same applies after 4).
In Examples 1-4, there is no change in a state, and it is thought that heat resistance improved by the effect of the polyester resin layer of a co-extrusion two-layer resin film. The nylon films alone of Comparative Examples 1 and 2 could not withstand a temperature of 180 ° C.

(High temperature and humidity resistance)
The film-like laminate before slitting was cut into a size of 50 mm × 50 mm and kept in an environment of a temperature of 40 ° C. and a humidity of 90% for 72 hours.
Table 4 shows the results. Δ in the evaluation column can be used as a silver thread by slitting the film after the test, but clearly shows a difference in appearance from the sample of ○ (the same applies to Table 5 and later).
In Examples 1 to 4, there is no change in the state, and it is considered that the polyester resin layer became a barrier and no metal discoloration occurred. In Comparative Examples 1-2, the metal vapor deposition layer discolored when the nylon film layer absorbed and released moisture.

(Resistance to mercerization)
Each slit thread was wound up to 10 m and immersed in an aqueous solution of sodium hydroxide (40 g / L) at 21 ° C. for 1 minute to evaluate whether mercerization is possible. The mercerizing process is a process generally performed to remove or whiten cotton stains, and when cotton is scoured and washed with a sodium hydroxide solution, the cotton stains are removed to give a white shining color.
Table 5 shows the results. When Al is used as a metal, it disappears by reacting with sodium hydroxide, and therefore it is known that mercerization cannot be applied to Al vapor-deposited products. This was the same in Examples 3 to 4 according to the present invention. When Ag was used as the metal, Example 2 was ◯, Example 1 was Δ, and Comparative Example 1 was ×. Example 1 and Example 2 differ in that the latter has an anchor coat, and it is considered that the adhesion between the polyester layer and the Ag thin film layer appears in the difference in the results.

(Acid dyeing property)
Each slit thread was wound up by 10 m and held in an acidic dyeing solution at 80 ° C. and 100 ° C. for 60 minutes. The acid dyeing solution was prepared by mixing 1 g / L of acetic acid, 0.5 g / L of amylazine D (Daiichi Kogyo Seiyaku Co., Ltd.), and 0.01 g / L of acid dye (Inoue Chemical Industry Co., Ltd.).
Table 6 shows the results.
In Examples 1 to 4, it was easily dyed even by low-temperature dyeing, post-dyeing was possible, and further, it was shown that the post-dyeing processability was excellent. Example 1 and Example 2 in which an Ag vapor deposition layer is used for the metal thin film are also excellent in luminance. In Comparative Examples 1 and 2, the low-temperature dyeing property was poor, and the metal vapor-deposited film was peeled off when dyeing at a high temperature.

1, 11 Polyamide layer 2, 12 Polyester layer 3, 13 Anchor coat layer 4, 14 Metal thin film layer 5, 15 Top coat layer 6 Adhesive layer 8, 18 Multilayer resin film

Claims (7)

A silver thread slit into a thin laminated film,
The laminated film has at least five layers of a polyamide layer, a polyester layer, a metal thin film layer, a topcoat layer, and an adhesive layer in this order,
The metal thin film layer, Ri A g or Rana,
The polyamide layer and the polyester layer state, and are not to form part or all of a multilayer resin film which is molded integrally by coextrusion,
The polyamide layer has a thickness of 3 to 15 μm,
The polyester layer has a thickness of 1 to 5 μm,
The silver thread , wherein the L ^* value of the reflection color of the obtained laminated film is 94.51 or more . A silver thread slit into a thin laminated film,
  The laminated film has at least five layers of a polyamide layer, a polyester layer, a metal thin film layer, a topcoat layer, and an adhesive layer in this order,
  The metal thin film layer is made of Al,
  The polyamide layer and the polyester layer form part or all of a multilayer resin film integrally formed by coextrusion,
  The polyamide layer has a thickness of 3 to 15 μm,
  The polyester layer has a thickness of 1 to 5 μm,
  L of the reflection color of the obtained laminated film ^* The value is 91.03 or more
Silver thread characterized by that. The laminated film, silver thread according to any one of claims 1 or 2, characterized in that it has a between the polyester layer and the metal thin film layer, further the anchor coat layer. The laminated structure of the laminated film, silver thread according to any one of claims 1 to 3, characterized in that symmetrical about said adhesive layer. The twisted yarn using the silver yarn as described in any one of Claims 1-4 . A woven fabric using the silver yarn according to any one of claims 1 to 4 and / or the twisted yarn according to claim 5 . A knitted fabric using the silver yarn according to any one of claims 1 to 4 and / or the twisted yarn according to claim 5 .

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