JP3435717B2 - Metallized sheets, camouflage materials, clothing and agricultural sheets - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal vapor-deposited sheet having excellent durability, a camouflage material, clothing and an agricultural sheet.

[0002]

2. Description of the Related Art Conventionally, a metal evaporated film is formed by protecting a metal foil formed by a vacuum evaporation method with a resin film such as a polyester film. At this time, a polyurethane resin is usually used as an adhesive. Met.

[0003]

However, an adhesive consisting only of such a polyurethane resin is weak in water resistance and heat resistance and has a drawback that the wet adhesion and the heat reflection property are significantly deteriorated. It is seen as a problem in areas such as car seats, sportswear and camouflage nets. In particular,
Metal foils such as aluminum, copper, and nickel have the drawbacks that they are weak against water and their heat reflection properties deteriorate immediately, and a protective film with excellent water resistance is required, but with conventional adhesives alone,
The wet adhesive strength was 1/2 or less of that when dried, and the washing resistance was poor, and as a result, the heat reflection property was also greatly reduced.

In view of such conventional defects, the present invention is to provide a metal vapor deposition sheet which is excellent in water resistance and adhesiveness and has durability of the heat reflection property of the metal vapor deposition film. It aims to provide durable camouflage materials, clothing and agricultural sheets.

[0005]

The present invention employs the following means in order to achieve the above object.

The metal vapor-deposited sheet of the present invention is a metal vapor-deposited sheet having a substrate, a metal vapor-deposited foil, and a protective film, the protective film containing a copolymer of vinyl chloride and vinyl acetate as a main component . And the vinyl chloride and vinyl acetate
The polymer is characterized by having a phosphoric acid group as a functional group , and the metal vapor deposition sheet of the present invention is a metal vapor deposition sheet having a substrate and a metal vapor deposition foil. In the above, the metal-deposited foil is bonded to a substrate through a copolymer of vinyl chloride and vinyl acetate , and the vinyl chloride is
The copolymer of vinyl acetate and vinyl acetate has a phosphate group as a functional group.
To is intended to, characterized in that, also, further metal deposition sheet of the present invention, the metal deposition sheet having a substrate and a metal deposition foil, the metal deposited foil, co-vinyl chloride and vinyl acetate It is sandwiched by a polymer in a sandwich structure , and the vinyl chloride and vinyl acetate
It is characterized in that the copolymer has a phosphoric acid group as a functional group .

The camouflage material, clothing and agricultural sheet of the present invention are characterized by being composed of the above metal vapor deposition sheet.

[0008]

When the metal foil is protected by a protective film made of a specific resin in a sheet obtained by adhering or transferring a metal vapor deposition film to a base material, the present invention is excellent in water resistance, which has been a conventional problem. It is a solution to the problem. further,
It has been clarified that such a resin joins the metal foil and the substrate with excellent adhesiveness, and that when the metal foil is sandwiched with the resin, water resistance and adhesiveness are simultaneously satisfied.

As the metal vapor deposition foil used in the present invention, for example, aluminum, nickel, copper, chromium and the like can be used. Among them, aluminum and copper are preferable because of their high heat ray reflection characteristics, and aluminum is more cost effective. The best material. In the present invention, a copolymer of vinyl chloride and vinyl acetate and a copolymer of vinyl chloride and vinyl acetate having a phosphoric acid group as a functional group are used as the protective film or the adhesive resin for the metal vapor deposition foil. By using the resin, the water resistance of the metal foil can be improved, and the adhesion between the metal foil and the substrate and the wet adhesion can be improved. The copolymerization ratio (monomer weight ratio) of the vinyl chloride and vinyl acetate copolymer is 80-90% vinyl chloride / 10-20% vinyl acetate from the viewpoint of adhesiveness to the metal foil and flexibility. desirable. In the present invention, a phosphoric acid ester having a carbon-carbon double bond copolymerizable with these monomers is preferably added to such a component in an amount of 0.01 to 5% by weight, more preferably 0.1 to 4% by weight. Copolymerization is preferable within the range.
The copolymerization ratio of the phosphate ester is preferably within the above range from the viewpoint of adhesiveness and water resistance.

The copolymerization ratio (monomer weight ratio) of the vinyl chloride / vinyl acetate copolymer is 80 to 90% vinyl chloride / 10 to 20% vinyl acetate from the viewpoint of adhesiveness to the metal foil and flexibility. Is desirable. In the present invention, a phosphoric acid ester having a carbon-carbon double bond copolymerizable with these monomers is preferably added to such a component, preferably 0.01
It is preferable to copolymerize in the range of ˜5 wt%, and more preferably 0.1 to 4 wt%. The copolymerization ratio of the phosphate ester is preferably within the above range from the viewpoint of adhesiveness and water resistance.

Examples of the phosphoric acid ester include 2-acid phosphooxyethyl acrylate and 2
-Acid phosphooxypropyl acrylate, 2-acid phosphooxyethyl methacrylate, 2-acid phosphooxypropyl methacrylate and the like can be used.

In this copolymer (hereinafter referred to as "specific copolymer"), when the proportion of vinyl chloride is large, the adhesive strength is low, and when the proportion of vinyl acetate is large, the flexibility is low and the brittleness tends to be present. .

The degree of polymerization of the specific copolymer is preferably 200 to 1000, more preferably 300 to 700.
Is. When the degree of polymerization is low, it tends to be brittle and inferior in flexibility. On the other hand, when the degree of polymerization is high, the viscosity becomes high and the coating process becomes difficult. The thickness of the resin film is
The thinner it is, the softer it is, the easier it is to fit on the fabric, and the better the adhesiveness. However, the film thickness is preferably 2 to 7 µ, and more preferably about 4 µ. If the resin film is extremely thin and has a thickness of 1 μm or less, coating unevenness tends to occur, which tends to cause partial adhesion failure. In addition, if the thickness of the resin film becomes thicker than 7 μ, the film itself becomes hard, it is difficult to fit on the substrate (film, cloth), and adhesion failure and flexibility tend to be poor. However, when the protective film constitutes the outermost surface layer, it may have a thickness of more than 7 μm.

Furthermore, by mixing polyurethane with the specific copolymer, it is possible to provide a sheet having high flexibility and improved durability such as bending and scuffing while maintaining adhesive strength. The ratio of polyurethane mixed with the specific copolymer is preferably 50:50 to 100: 0, more preferably 70:30 to 90:10. As a mixing method, there is a method of laminating with a blend. The lamination makes it a little harder, but the adhesion and water resistance are stronger.
Here, the term “laminate” means to laminate the specific copolymer via a polyurethane resin. That is, a polyurethane resin is used as an adhesive.

By including a colorant (dye, pigment) on one surface (outermost surface layer) of the protective film, various colors can be imparted, and a highly fashionable product can be provided. . In particular, by incorporating a near-infrared pigment whose near-infrared reflectance matches that of trees, soil, etc., a sheet having excellent far-infrared thermal emissivity can be provided. For example, the pigment-coated product can provide a camouflage material (mesh) having an excellent camouflage effect on visible, near-infrared radar waves, and far-infrared rays. Examples of such near infrared pigments include yellow lead, titanium oxide,
Special pigments such as carbon black and iron oxide are used by mixing them. With this pigment, the near-infrared reflectance in the near-infrared region of 0.6 to 1.5 μ can be approximated to that of a natural background, and as a result, an excellent camouflage effect can be achieved.

The case of coating the specific copolymer resin has been described above, but the same thickness condition is adopted when the specific copolymer resin is used as an adhesive when laminating a metal vapor deposition foil. The metal vapor deposition foil film is dry laminated with an adhesive and transferred to a substrate. In this case, when the metal vapor deposition foil is protected by a specific copolymer resin film or is sandwiched, another resin other than the above can be used as the adhesive. The thickness of the adhesive is not particularly limited, but the total thickness of the protective film and the adhesive layer is preferably 5 to 5.
The thickness is 8 μ, and the thickness of 15 to 50% thereof is preferable from the viewpoint of hardness and durability.

In the present invention, the substrate used is not limited as long as it is a sheet-like material such as a film, a non-woven fabric, a knitted fabric or a woven fabric. It is preferable to subject the base material to a smoothing process such as calendering or resin processing because a stronger adhesive force is obtained.

Next, an example of the metal vapor deposition sheet of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view showing a cross section of an example of the metal vapor deposition sheet of the present invention. In the figure, 1 is a substrate (film, cloth), 2 is an adhesive, 3 and 5 are protective films, and 4 is a metal deposition foil. In this example, the metal vapor deposition foil 4 is protected from both front and back sides by protective films 3 and 5 made of the specific copolymer resin film of the present invention, and is provided with oxidative corrosion resistance and water resistance. The protective film 3 may be formed by coating the metal vapor deposition foil 4 on the base material 1 and then coating it, or may be applied by a metal vapor deposition film as shown in FIG. However, it is easier to obtain high heat ray reflectivity when formed by the above-mentioned coating, so that there is an advantage that the color can be freely selected and the versatility is excellent. In the case of a camouflage net, green and brown pigments are coated by this method.

FIG. 2 is a schematic view showing a cross section of an example of a metal vapor deposition film used for transfer. 3 is an adhesive, 4 is a metal vapor deposition foil, 5 is a protective film, and 6 is a film. However, 3 and 5 are the same resin, and the resin film made of the specific copolymer resin film of the present invention is used.

FIG. 3 is a schematic view showing an example of the metal vapor deposition foil transfer process of the present invention.

First, the metal vapor-deposited film 7 is coated with an adhesive by a roll 8 and the solvent is volatilized by a drier 9, and then the coated surface is stuck to the substrate 1 to form a roll 1.
After pressing 0, peel off the film and roll 1 again
After being pressed with No. 1, it is wound with a take-up roll 12. Then 4
Aging is performed in a greenhouse at 0 ° C. for 24 hours to prepare a metal vapor deposition sheet by a transfer method.

The above metal vapor deposition film can be manufactured by the following method.

That is, the film is coated with a release agent, and then a mixed solution of a colorant and a specific copolymer resin is coated thereon in an amount of 2 to 20 μm according to the application.

Next, this coating film is passed through a vapor deposition apparatus to prepare a metal vapor deposition film. The specific copolymer resin is further coated on the metal foil of the obtained metal vapor deposition film to a thickness of about 2 to 7 μm to form a protective film.

The metal vapor-deposited sheet obtained by this method is provided as a metal vapor-deposited foil of several hundred angstroms protected from both sides by a specific copolymer resin film.

Next, the camouflage material of the present invention is manufactured by using the above-mentioned metal vapor deposition sheet. Among the sheets, far infrared thermal emissivity is in the range of 0.4 to 0.9. Together, it was manufactured to achieve a thermal camouflage effect in infrared images in the far infrared wavelength region 3-14μ. The camouflage material of the present invention similarly achieves an excellent camouflage effect in the visible light, near infrared, and radar wave wavelength regions. The far-infrared thermal emissivity described above can be adjusted by the film thickness of the protective film. When the film thickness is thin, low thermal emissivity can be provided, and as the film thickness is high, high thermal emissivity can be provided. By adjusting the film thickness, to create a sheet having various thermal emissivity, by forming a camouflage pattern adjacent to those having a similar thermal emissivity, to cause a blur effect on far infrared rays, Achieves a camouflage effect very close to the background temperature.

Next, the garment of the present invention is a cloak, coat, garment or the like using the above metal vapor deposition sheet,
It is not restricted by its form. This clothing has a far-infrared thermal emissivity of preferably 0.5 among the above metal vapor deposition sheets.
Hereinafter, a sheet having a low thermal emissivity of 0.2 to less than 0.4 is more preferably used. The metal vapor-deposited sheet used for this garment may be composed of a sheet having a constant thermal emissivity, but for a particular place where heat is likely to accumulate or summer clothing where the outside air temperature is high, a sheet having a high thermal emissivity It is better to configure with. For example, firefighting clothes and sportswear are preferably made of a sheet having a high thermal emissivity close to about 0.2.

Further, the agricultural sheet of the present invention is a sheet having a low thermal emissivity of far infrared ray emissivity of preferably 0.4 or less, more preferably 0.2 to 0.3 among the above-mentioned metal vapor deposition sheets. Is preferably used. This is based on the fact that the object is originally a plant and therefore does not require so high heat radiation. For example, even an agricultural house does not need a sheet having such a high heat emissivity because it reaches a room temperature of up to about 80 ° C. in summer to some extent.

[0030]

EXAMPLES The present invention will be described in more detail with reference to Examples.

The following evaluation methods were adopted in the examples.

A. Surface-peeling state: Surface-peeling state The surface-peeling state on the metal vapor-deposited surface after 30 minutes of normal-temperature water washing with a household washing machine was observed.

◯: No change Δ: Partial peeling ×: Most peeling B. Adhesive peel strength: The same fabric or film was stuck with an adhesive, and the peel strength on the metal vapor deposition surface in a dry state and a wet state after immersion in water for 12 hours was measured.

C. Sunshine weather meter (SW
M) Changes in emissivity (far infrared thermal emissivity) after irradiation for 500 hours were measured. This emissivity is a rating scale showing the heat ray (far infrared) reflectance, and the lower the radiation, the better the heat ray reflectance.

The amount of blue coloring and the protective film thickness were adjusted so that the emissivity was 0.40, and the film was processed and measured with a D AND S AERD type emissometer (manufactured by D AND S).

Example 1 A copolymer obtained by blending a polyester film with 80% by weight of vinyl chloride and 20% by weight of vinyl acetate and 3% by weight of 2-acid phosphooxyethyl methacrylate and copolymerizing the mixture (JIS K-6721). Average degree of polymerization by: 400) 5
It was coated to a film thickness of μ.

Aluminum was vapor-deposited on this film as a metal, and the above-mentioned copolymer was coated as a protective film to a thickness of 5 μm to prepare a metal vapor-deposited film.

The results of evaluation of the metal vapor deposition film obtained are shown in Table 1.

Example 2 A polyester film was coated with a release agent,
In addition, a colored resin obtained by mixing the same copolymer as in Example 1 with a blue colorant except that the average degree of polymerization was 900
It was coated to a film thickness of μ.

On the coating film of this film,
Aluminum was vapor-deposited as a metal, and the above-mentioned copolymer was further coated as a protective film in a thickness of 5 μm to prepare a metal vapor-deposited film.

Using the apparatus shown in FIG. 3, the above metal vapor deposition film was coated with a two-pack type polyester resin adhesive and dried.
The film was attached to a polyester woven fabric whose surface was smoothed by resin processing, pressed with a rubber roll, peeled off the film, and then re-pressed with a rubber roll to obtain a metal vapor deposition sheet on which a metal vapor deposition film was transferred.

The results of evaluation of the obtained metal vapor deposition sheet are shown in Table 1.

Examples 3 and 4 The same processing as in Example 1 was carried out except that the various conditions shown in Table 1 were adopted to obtain metal vapor deposition sheets.

However, the specific copolymer resin used in Example 2 was used, and a mixture of 85 parts of this copolymer resin with 15 parts of polyurethane was used.

The results of evaluation of the obtained metal vapor deposition sheet are shown in Table 1.

Example 5 In Example 3, 1% by weight of 2-acid phosphooxyethyl methacrylate was blended as a specific copolymer and copolymerized (average degree of polymerization according to JIS K-6721: 400).
The same process was carried out to obtain a metal vapor-deposited sheet except that the metal vapor deposition sheet was used.

The results of evaluation of the obtained metal vapor deposition sheet are shown in Table 1.

[0048]

[0049]

[0050]

Table 1 shows the results of evaluation of the obtained metal vapor deposition sheet.

[0052]

[Table 1] As can be seen from Table 1, Examples 1 to 5 have good coating processability, adhesiveness, peel strength and emissivity. Contrary to this, it was confirmed that Comparative Example 1 had a low peeling strength and could easily peel off when wet.

Example 6 In Example 2, a colored resin in which a near infrared pigment (Dailac color: manufactured by Dainippon Ink and Chemicals, Inc.) was mixed in place of the blue colorant was coated, and light green, dark green,
A brown metallized sheet was processed. Each film thickness is 5μ,
8 μ and 11 μ were coated. However, 40% of each film thickness was applied and laminated with a polyester polyurethane resin as an adhesive.

That is, when aluminum is vapor-deposited as a metal on the colored resin coating film and the above-mentioned copolymer is coated as a protective film while changing the film thickness to various values, the respective film thicknesses are previously adjusted. On the other hand, 40% of polyester-based polyurethane resin was applied.

The far infrared thermal emissivity of the obtained sheet is
Sheets of 0.40, 0.60, 0.75 were obtained. A far-infrared camouflage net was prepared by coloring and combining the sheets so that the ratio of light green was 50%, dark green was 40%, and brown was 10%. The sheet characteristics of these three types of sheets were evaluated in the same manner as in the above-mentioned examples. The results are shown in Table 1.

As is clear from Table 1, a sheet having more excellent adhesiveness than Example 2 and having a small change in thermal emissivity and excellent durability was obtained. Also, the detection wavelength 8
When observed outdoors using an infrared imaging device (Infra Eye 560: manufactured by Fujitsu Ltd.) of ˜14 μ, a far infrared image mixed with a forest background was obtained. Similarly, when observed outdoors using an infrared night-vision device (manufactured by NEC) with a detection wavelength of 1.2μ, a near-infrared camouflage image was obtained. It was confirmed that each achieved excellent camouflage effect.

Example 7 Instead of laminating the polyester-based polyurethane resin in Example 6 , the same amount of the polyurethane resin was mixed and coated.

As a result, the sheet characteristics were superior to those of Example 2, but slightly inferior to those of Example 6, and other changes in thermal emissivity and durability were the same as those of Example 6. As a result, the result of outdoor observation was the same as that of Example 6.

Example 8 Except that the outermost (front surface) protective film has a thickness of 2 μm,
A metal-deposited woven fabric (far-infrared thermal emissivity: 0.25) obtained in the same manner as in Example 2 was used as the lining, and the resin coating side of the woven fabric was used together with the outer material to prepare the front body of the coat. The back body was sewn, and the sleeve sewn with the above-mentioned outer material having the cupra lining was attached to the back body, and then the collar was attached to obtain a winter coat. This cold-prevention coat had excellent heat retention.

Example 9 The vapor-deposited metal film obtained in Example 1 was spread on the wall of a gable type agricultural house, the protective film side being the inside of the house and the polyester film side being the outside. In this farm house,
The light captured from the roof was reflected on the aluminum foil of the metallized film on the wall surface, and the effect of effectively irradiating the entire surface of the plant with light was achieved. Example 10 The metal vapor-deposited film obtained in Example 1 was used as an agricultural sheet by laying it on a vegetable cultivation soil with the protective coating side on the ground side and the polyester film side on the outside. That is, when the film was coated on the ridges of the soil, a seed planting hole having a diameter of about 10 cm was provided in the center of the film, and seed was planted in this hole. As a result, it was possible to grow vegetables quickly and to harvest dark-colored vegetables.

[0061]

EFFECTS OF THE INVENTION The present invention provides a metal vapor-deposited sheet which has a very high adhesive force, particularly an adhesive force when wet, and has little change in the heat radiation characteristics during use with time and has good durability. You can Further, the present invention can provide a camouflage material, a garment and an agricultural sheet which are excellent in durability and heat radiation characteristics by using such a sheet.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of an example of a metal vapor deposition sheet of the present invention.

FIG. 2 is a cross-sectional view showing an example of a metal vapor deposition film used in a transfer method of an example of the metal vapor deposition sheet of the present invention.

FIG. 3 shows an example of the metal transfer process of the present invention.

[Explanation of symbols]

1: Cloth 2: Adhesive 3, 5: protective film 4: Metal evaporated foil 6: Film 7: Metallized film 8: Coating roll 9: Dryer 10, 11: Press roll 12: Winding roll

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Claims (15)

(57) [Claims] 1. A metal deposition sheet having the base material and the metallized foil and the protective film, the protective film state, and are not mainly composed of a copolymer of vinyl chloride and vinyl acetate, and the
A copolymer of vinyl chloride and vinyl acetate is used as a functional group.
Metallized sheet, characterized in der Rukoto having a phospho groups. 2. A metal vapor-deposited sheet having a substrate and a metal vapor-deposited foil, wherein the metal vapor-deposited foil is bonded to the substrate through a copolymer of vinyl chloride and vinyl acetate , and
A copolymer of vinyl and vinyl acetate has phosphoric acid as a functional group.
Metallized sheet, characterized in der Rukoto has a group. 3. A metal vapor deposition sheet having a substrate and a metal vapor deposition foil, wherein the metal vapor deposition foil is sandwiched by a copolymer of vinyl chloride and vinyl acetate in a sandwich structure .
And the copolymer of vinyl chloride and vinyl acetate
Metallized sheet, characterized in der Rukoto those having a phosphoric acid group as a functional group. Wherein said phosphoric acid group, a carbon - metallized sheet according to any one of claims 1 to 3 is a phosphate ester derived from a phosphoric acid ester 0.01-5% by weight of carbon double bonds. 5. The metal vapor deposition sheet according to claim 1, wherein the copolymer is a copolymer of 80 to 90% by weight of vinyl chloride and 10 to 20% by weight of vinyl acetate. 6. The metal vapor deposition sheet according to claim 1, wherein the copolymer has a degree of polymerization of 200 to 1000. 7. the protective film, a polyurethane resin 10-5
0% mixed resin composition obtained according to claim 1-6 Neu
The metal vapor-deposited sheet according to the above. 8. The metal vapor deposition sheet according to claim 1, wherein the protective film is laminated via a polyurethane resin layer. 9. The method according to claim 8 , wherein the protective film contains a pigment.
The metal vapor deposition sheet according to any one of 1 . 10. A consists of a substrate and the deposited metal foil and the protective film, and Ri resin der the protective film is composed mainly of a copolymer of vinyl chloride and vinyl acetate, and said salt of vinyl acetate
The vinyl copolymer has a phosphoric acid group as a functional group.
Impersonation material characterized by being composed Nodea Ru metal deposition sheet. 11. The metallized sheet is 0.4 to 0.9
The camouflage material according to claim 10, which has a far-infrared thermal emissivity of. 12. consists of a substrate and the deposited metal foil and the protective film, and Ri resin der the protective film is composed mainly of a copolymer of vinyl chloride and vinyl acetate, and said salt of vinyl acetate
The vinyl copolymer has a phosphoric acid group as a functional group.
Clothing, characterized in that it is constituted by Nodea Ru metal deposition sheet. 13. The clothing according to claim 12 , wherein the metal vapor-deposited sheet has a far-infrared thermal emissivity of 0.5 or less. 14. consists of a substrate and the deposited metal foil and the protective film, and Ri resin der the protective film is composed mainly of a copolymer of vinyl chloride and vinyl acetate, and said salt of vinyl acetate
The vinyl copolymer has a phosphoric acid group as a functional group.
Agricultural sheeting, characterized in that it is constituted by Nodea Ru metal deposition sheet. 15. The agricultural sheet according to claim 14 , wherein the vapor-deposited metal sheet has a far infrared thermal emissivity of 0.4 or less.