JP2632775B2 - Laminating film for easy sticking and sticking product sticking it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can be easily adhered to a target surface such as a glass surface with water, and in the adhered state, it is difficult for moisture to enter the inside from the surface side. The present invention relates to an easy-to-adhere laminating film having a property that moisture easily comes out of the film. The present invention also relates to a sticking product on which the sticking laminated film is stuck.

[0002]

2. Description of the Related Art By attaching a functional film to a glass surface, it is possible to adjust the transparency, impart color, cut ultraviolet rays, cut infrared rays, impart anti-fogging properties, prevent glare, prevent static electricity, decorate, break. Attempts have been made to prevent scattering at the time.

As a method for attaching a film to a glass surface, there are a method using an adhesive, a method using an adhesive, a method using water, a method using static electricity, and the like.

[0004]

However, it is surprisingly difficult to attach a film to a glass surface. That is,
The method of using an adhesive is such that even a skilled person is liable to wrinkle, the adhesive flows to contaminate the glass surface other than the bonding site, and the water is difficult to volatilize, so a considerable number of days is required until complete adhesion. Is required. The method using an adhesive has problems such as difficulty in positioning because it cannot be displaced after temporary attachment and easy entry of air bubbles. In the method using water, the kind of applicable target film is limited, and the adhesive strength is often poor. The method using static electricity has a limitation that it cannot be practically applied to a glass surface.

[0005] As described above, even a skilled person has various difficulties in attaching a film to a glass surface.
It is not uncommon for the sticking operation cost to be higher than the film cost. Rather, the sticking cost is usually much higher than the film cost.

[0006] In any of the above-mentioned sticking methods, when the temperature rises, the sticked film expands and the inside is reduced in pressure, so that air enters through the membrane and the sticked film tends to swell. There is.

[0007] Under such a background, the present invention can easily adhere to a target surface such as a glass surface with water,
Easy positioning, no wrinkles or air bubbles, and in the adhered state, it is difficult for water to enter the inside from the surface side, while water moves from the inside to the surface side Having a property, and further providing an easy-sticking adhesive laminated film that is unlikely to cause swelling after application,
Further, it is an object of the present invention to provide a bonded product to which the laminated film for bonding is attached.

[0008]

Means for Solving the Problems The laminated film for easy sticking according to the present invention comprises a high moisture permeability thin film layer (A) and a low moisture permeability thin film layer.
(B), wherein the high-moisture-permeable thin film layer (A) side is adhered to the target surface (O), and the high-moisture-permeable thin film layer (A) As the moisture-permeable thin film layer (B), these layers have a temperature of 40 according to JIS Z0208.
° C., a moisture permeability at a relative humidity of ^{90% RH (g / m 2} · 24hr)
Are Pa and Pb, respectively, where Pa ≧ 300 (1) Pb ≧ 100 (2) Pa ≧ 3 × Pb (3) It is assumed that.

Further, in the adhesive product of the present invention, the above-mentioned easy-adhesive laminating film is attached to the target surface (O) such that the high-moisture-permeable thin film layer (A) side is the target surface (O). It is what you wear.

Hereinafter, the present invention will be described in detail.

[0011] The laminated film for easy sticking of the present invention comprises:
It has a laminated structure of a high moisture permeability thin film layer (A) and a low moisture permeability thin film layer (B). Then, the high-moisture-permeable thin film layer (A) side is the side to be adhered to the target surface (O).

The moisture permeability Pa of the highly moisture-permeable thin film layer (A) is
As in (1), it is necessary to be 300 g / m ² · 24 hr or more. Since the low moisture permeability thin film layer (B) is also required to have a certain degree of moisture permeability, the moisture permeability needs to be 100 g / m ² · 24 hours or more as described in (2) above. When the moisture permeability Pb of the low moisture permeability thin film layer (B) is smaller than the above range, a film having the desired moisture transfer property cannot be obtained even if the high moisture permeability thin film layer (A) is laminated.

Further, the high-moisture-permeable thin film layer (A) and the low-moisture-permeable thin film layer (B) satisfy the above condition (3), that is, the high-moisture-permeable thin film layer (A) Must be at least three times (preferably at least four times) greater than the moisture permeability Pb of the low moisture permeability thin film layer (B).

Examples of the highly moisture-permeable thin film layer (A) include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, N-methoxy-6-nylon, polyacrylate,
Polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, carboxymethylcellulose, methylcellulose, cellophane, natural polymers or processed products thereof (gelatin, casein, glue, albumin, alginates, pectin salts,
Chitosan, chitin, pullulan, zein, keratin, etc.),
Examples of the film layer include polyester urethane, polyurethane, and a UV-curable resin having a hydrophilic group. Among them, a water-soluble film layer is preferable. Of particular interest among the high moisture permeable thin film layers (A) are silicon-containing water-soluble polymer layers such as silicon-modified polyvinyl alcohol in which a silicon-containing monomer is introduced into the molecule by copolymerization or graft polymerization.

The above high moisture permeability thin film layer (A) has a gas permeability of 3 in terms of oxygen permeability (measured according to ASTM D-1434-75).
0cc ・ / 24hr ・ m ²・ atm or less, preferably 20cc ・ / 24
hr · m ² · atm or less, in particular ^{10cc · / 24hr · m 2 ·} atm or less, inter alia is desirably less ^{5cc · / 24hr · m 2 ·} atm. When a material having a low gas permeability is used as described above, air does not enter through the membrane even when the temperature changes after application, and therefore, the attached film does not bulge.

Examples of the low moisture permeable thin film layer (B) include polycarbonate, crosslinked phenoxy ether resin, ultraviolet curable resin, polysulfone, nylon, cellulose propionate, and ethylene-vinyl alcohol having a relatively high ethylene content. Film layers of polymers, polystyrene, polyimide, polyester, polyether and the like can be mentioned.

However, whether the layer is a high-moisture-permeable thin film layer (A) or a low-moisture-permeable thin film layer (B) is relative, and the moisture permeability is greatly affected by the film thickness and the copolymer composition. Therefore, even the same polymer may belong to the high moisture permeability thin film layer (A) or the low moisture permeability thin film layer (B). In addition, even if it is considered that the film usually has an extremely small moisture permeability, the moisture permeability increases when the film thickness is reduced.In general, the moisture permeability increases when the film thickness is increased even though the moisture permeability is considered to be extremely large. Become smaller. Therefore, the above example is for convenience only.

The high-moisture-permeable thin film layer (A) can be not only a single layer but also a multilayer, and similarly, the low-moisture-permeable thin film layer (B) can be not only a single layer but also a multilayer.

The lamination can be performed by forming one layer on one layer by a method such as casting. In this case, in order to improve the interlayer adhesion, the upper layer can be cast via an anchor coating layer belonging to the high moisture permeability thin film layer (A) or the low moisture permeability thin film layer (B). It is possible to form a high-moisture-permeable thin film layer (A) or a low-moisture-permeable thin film layer (B) using commercially available high-moisture-permeable thin film layers (A) and low-moisture-permeable thin film layers (B). It is also preferable to perform adhesive lamination through an adhesive layer. High moisture permeability thin film layer
The lamination of (A) and the low moisture permeable thin film layer (B) can also be performed by a method such as co-extrusion coating or extrusion coating.

Although the thickness of each layer is not particularly limited, the high moisture permeable thin film layer (A) has a thickness of about several μm to 500 μm,
(B) is often about 1 to 100 μm.

[0021] The laminated film for easy adhesion of the present invention comprises:
Adjustment of transparency, addition of color, UV cut, infrared cut, electromagnetic wave shield, anti-fog property, anti-glare, anti-static, decoration, prevention of scattering at breakage, sensor on glass surface etc. It is useful as a film for the purpose of imparting functionalities such as a deodorizing effect and an aromatic effect. For this reason, the high moisture permeability thin film layer (A) and the low moisture permeability thin film layer (B) include a concealing substance, a coloring agent, an ultraviolet absorber, an ultraviolet reflector, an infrared absorber, an infrared reflector, a surfactant, Inhibitor, polarizing substance, liquid crystal substance, photochromic material, thermosensitive substance,
Radiation-sensitive substances, deodorants, functionalizing substances such as fragrances can be blended, and as these layers,
Stretched, doped, metal-deposited or sputtered layers, or provided with a coating layer can also be used.

[0022]

When the laminated film of the present invention is used, the water-permeable thin film layer (A) is coated with water, and then the water-permeable thin film layer (A) is coated with glass. It is attached to the target surface (O) such as a surface to give functionality to the target surface (O).
“Applying water” refers to application of water, spraying of water vapor, contact with a high-humidity atmosphere, and the like. Thereby, the sticking operation can be performed smoothly without wrinkles or bubbles. It is also possible to perform positioning after temporarily attaching.

The laminated film is formed by adopting a combination that satisfies the above-mentioned relations (1), (2) and (3) as the high moisture permeability thin film layer (A) and the low moisture permeability thin film layer (B). Because of this structure, when it is attached to the target surface (O), it is difficult for moisture to enter the inside from the surface side (low moisture permeability thin film layer (B) side), while the inside (high moisture permeability) From the thin film layer (A) side, there is a unique effect that moisture easily flows out to the surface side (low moisture permeability thin film layer (B) side). In other words, high moisture permeability thin film layer
Moisture migrates in one direction from the (A) side to the low moisture permeability thin film layer (B) side. Therefore, the water used at the time of adhering is removed from the surface side in a short time through the laminated film, while moisture outside (for example, inside a room or a car) is hardly absorbed into the laminated film that is adhered.

If a thin film layer having low gas permeability is selected and used as the high moisture-permeable thin film layer (A), air does not enter through the membrane even when the temperature changes after the application, and therefore the swelling of the adhered film occurs. Will not occur.

[0025]

The present invention will be further described with reference to the following examples. Hereinafter, "parts" refers to parts by weight.

Example 1 FIG. 1 is a cross-sectional view showing an example of the easily adhered adhesive laminated film of the present invention, and shows a case where the laminated film is adhered to a target surface (O). The white arrow in FIG. 1 indicates the direction of water transfer.

40 parts of a phenoxy ether resin (manufactured by Union Carbide Co.), 40 parts of methyl ethyl ketone, 40 parts of a 75% solution of an adduct of tolylene diisocyanate and trimethylolpropane (Coronate L manufactured by Nippon Polyurethane Co., Ltd.), and ultraviolet light A phenoxy ether resin-based resin solution comprising 1 part of an absorbent (Tinuvin P manufactured by Ciba Geigy) was prepared.

Thickness 7 as an example of the high moisture permeability thin film layer (A)
0 μm silicon-modified polyvinyl alcohol film (“R-1130” manufactured by Kuraray Co., Ltd., oxygen permeability (AS
TM D-1434-75 measured according to): 1cc · / 24hr · m 2 · atm
On one side of the following), the above-mentioned phenoxy ether resin-based resin solution was cast using an applicator, dried at a temperature of 80 ° C. for 5 minutes, and then cured at a temperature of 120 ° C. for 20 minutes.
The low moisture permeability thin film layer (B) having the thickness shown in Table 1 was formed.

As a result, the easily adhered adhesive laminated film shown in FIG. 1 was obtained. Table 1 shows the measurement results of the moisture permeability (g / m ² · 24 hr) of this laminated film. The moisture permeability is J
ISZ0208 (measured at a temperature of 40 ° C. and a relative humidity of 90% RH based on the moisture permeability test method (cup method) of the moisture-proof packaging material. The moisture permeability Pa of the layer (A) alone film,
The moisture permeability Pb of the layer (B) alone film is as follows. Layer (A) alone film of moisture permeability Pa Thickness 70μm: 2500g / m ² · 24hr more layers (B) alone film of moisture permeability Pb thickness 8μm: 180g / m ² · 24hr Thickness 15μm: 130g / m ² · 24hr

[0030]

[Table 1] Layer (A) / layer (B) layer (A) → a layer (B) direction of the layer (B) → a layer (A) thickness in the direction of (μm / μm) moisture permeability (g / m ² · 24hr) Moisture Permeability ^{(g / m 2 · 24hr)} 70/4 670 185 70/6 380 110 70/10 120 55 70/15 116 30

From Table 1, it can be seen that the moisture permeability in the layer (A) → layer (B) direction is large, and that the moisture permeability in that direction is significantly larger than that in the layer (B) → layer (A) direction. I understand.

Water is applied with a sponge to the highly moisture-permeable thin film layer (A) side of the above-mentioned easy-adhesive laminating film, and then the highly moisture-permeable thin film layer (A) side is applied to the target surface (O). Affixed to a glass surface as an example. The sticking operation was easy, and the sticking could be performed without generating wrinkles or bubbles without skill. The water at the time of sticking was volatilized in the atmosphere through the low moisture permeability thin film layer (B) within several hours. Further, the surface of the low moisture vapor permeable thin film layer (B) after application was high in hardness (2H in pencil hardness) and had scratch resistance, so that scratching could be effectively prevented. Further, the adhered film did not swell even when the temperature changed.

COMPARATIVE EXAMPLE 1 On one surface of the silicon-modified polyvinyl alcohol film of Example 1 as an example of the high-moisture-permeable thin film layer (A), methanol, glycol ether, acetic acid and water were used as solvents in a weight ratio of 51: 17: 2. : A silicone resin solution having a resin content of 23% by weight used in a ratio of 7 was cast using an applicator, dried at a temperature of 60 ° C for 5 minutes, and then cured at a temperature of 100 ° C for 7 minutes. A low moisture permeability thin film layer (B ') was formed.

The moisture permeability (g / m ² · 24
hr) are shown in Table 2. The humidity Pa of the layer (A) single film and the moisture permeability Pb 'of the layer (B') single film are as follows. Layer (A) Moisture permeability Pa of single membrane 70 μm thick: 2500 g / m ² .24 hr or more Layer (B ′) Moisture permeability Pb ′ single membrane 6 μm: 25 g / m ² .24 hr

[0035]

[Table 2] Layer (A) / layer (B ') a layer of (A) → a layer (B') direction of the layer (B ') → a layer (A) thickness in the direction of (μm / μm) moisture permeability (g / m ² · 24hr ) moisture permeability ^{(g / m 2 · 24hr)} 70/2 36 30 70/4 26 31 70/6 25 41

From Table 2, it can be seen that the moisture permeability in the layer (A) → layer (B ′) direction and the moisture permeability in the layer (B ′) → layer (A) direction are both small, and the moisture permeability in both directions is not so different. You can see that. This is because the moisture permeability of the low moisture permeable thin film layer (B ') made of a silicone resin film is small, so that moisture transfer property does not actually appear regardless of the lamination of the high moisture permeable thin film layer (A). Means.

Water is applied to the high moisture permeable thin film layer (A) side of the laminated film with a sponge, and then the high moisture permeable thin film layer is applied.
When the (A) side is adhered to a glass surface as an example of the target surface (O), water at the time of adhering is not easily removed, and after 3 days, a force in a displacing direction is applied to the adhered film surface. , The adhesive film was wrinkled.

Example 2 FIG. 2 is a cross-sectional view showing another example of the easy-adhesive laminating film of the present invention, and shows a case where the film is adhered to the target surface (O). The white arrow in FIG. 2 indicates the direction of water transfer.

Thickness 7 as an example of the high moisture permeability thin film layer (A ₁ )
A 0 μm silicon-modified polyvinyl alcohol (used in Example 1) film and a 7 μm-thick ultraviolet absorber-containing nylon 6 film as an example of the low moisture permeable thin film layer (B) were mixed with N-methoxy-6-nylon. Was laminated by using the aqueous solution of the above as an adhesive and dried. The formed adhesive layer becomes a high moisture permeability thin film layer (A ₂ ) having a thickness of 5 μm.

Thus, (A ₁ ) / (A ₂ ) / (B) shown in FIG.
Thus, an easily adhered adhesive laminated film having the following layer constitution was obtained. The measurement results of the moisture permeability (g / m ² · 24 hr) of this laminated film were as follows. Layer (A ₁ ) → Layer (A ₂ ) → Layer (B) direction 440 g / m ²・ 24 hr Layer (B) → Layer (A ₂ ) → Layer (A ₁ ) direction 130 g / m ²・ 24 hr

The moisture permeability Pa of the layer (A ₁ ), (A ₂ ) alone membrane,
The moisture permeability Pb of the layer (B) alone film is as follows. Layer (A ₁ ) Moisture permeability Pa thickness of single film 70 μm: 2500 g / m ² · 24 hr or more Layer (A ₂ ) Moisture permeability Pa thickness of single film 5 μm: 2200 g / m ² · 24 hr Layer (B) Moisture permeability of single film Pb thickness 7μm: 400g / m ² · 24hr

The high humidity thin layer of easily bonded wear resistant laminate film according to the after applying water with a sponge in (A ₁₎ side, the high humidity thin layer of (A ₁₎ side target surface (O) Affixed to a glass surface as an example. The sticking operation was easy, and the sticking could be performed without generating wrinkles or bubbles without skill. The water at the time of application was volatilized in the atmosphere through the low moisture permeability thin film layer (B) within several hours. Further, the adhered film did not swell even when the temperature changed.

Example 3 Polyvinyl alcohol film having a thickness of 70 μm as an example of the high moisture vapor-permeable thin film layer (A) (degree of polymerization 1100, degree of saponification 88 mol%, oxygen permeability (measured according to ASTM D-1434-75) ) 1 cc · / 24 hr · m ² · atm or less, blended with an ultraviolet reflective agent), 100 parts of an epoxy acrylic resin (“V-254PA” manufactured by Nippon Steel Chemical Co., Ltd.) and 1 part of benzophenone were added. The ultraviolet-curable resin liquid was cast using an applicator, and then irradiated with ultraviolet rays to form a low moisture-permeable thin film layer (B) having a thickness of 8 μm.

As a result, an easily adhered laminated film having the layer constitution of (A) / (B) shown in FIG. 1 was obtained. The measurement results of the moisture permeability (g / m ² · 24 hr) of this laminated film were as follows. The moisture permeability Pa of the layer (A) having a thickness of 70 μm alone is 2500 g / m ² · 24 hr or more, and the moisture permeability Pb of the layer (B) having a thickness of 8 μm is 170 g / m ² · 24 hr. Layer (A) → a layer (B) Direction 320g / m ² · 24hr layer (B) → a layer (A) direction 90g / m ² · 24hr

Water is applied with a sponge to the highly moisture-permeable thin film layer (A) side of the above-mentioned easy-adhesive laminating film, and the high moisture-permeable thin film layer (A) side is applied to the target surface (O). Affixed to a glass surface as an example. The sticking operation was easy, and the sticking could be performed without generating wrinkles or bubbles without skill. The water at the time of sticking was volatilized in the atmosphere through the low moisture permeability thin film layer (B) within several hours. Further, the surface of the low moisture vapor permeable thin film layer (B) after application was high in hardness (4H in pencil hardness) and had scratch resistance, so that scratching could be effectively prevented. Further, the adhered film did not swell even when the temperature changed.

[0046]

According to the present invention, the high moisture permeable thin film layer (A)
And (1), (2),
Since the laminated film is configured using a combination that satisfies the relationship of (3), it can be easily adhered to the target surface (O) such as a glass surface with water, alignment is easy, and wrinkles are obtained. No air bubbles are generated.

Moreover, in the adhered state, it is difficult for moisture to enter the inside from the surface side (the low moisture permeable thin film layer (B) side).
On the other hand, it has a peculiar effect that moisture easily comes out from the inside (high moisture permeability thin film layer (A) side) to the surface side (low moisture permeability thin film layer (B) side). Water is removed from the surface side in a short time, while moisture from the outside (for example, in a room or in a car) is difficult to be absorbed into the laminated film attached.

When a material having a small gas permeability is selected and used as the high-moisture-permeable thin film layer (A), air does not enter through the membrane even when the temperature changes after the application, and therefore the swelling of the attached film occurs. Will not occur.

Therefore, according to the present invention, a functional film can be easily set on the target surface (O) such as a glass surface.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of an easily adhered laminated film according to the present invention, in which the laminated film is adhered to a target surface (O).

FIG. 2 is a cross-sectional view showing another example of the easy-to-adhere laminating film of the present invention, showing a case where the laminated film is adhered to a target surface (O).

[Explanation of symbols]

(A), (A ₁ ), (A ₂ )… High moisture permeability thin film layer (B)… Low moisture permeability thin film layer (O)… Target surface

Claims (6)

(57) [Claims] 1. A thin film layer having high moisture permeability (A) and a thin film layer having low moisture permeability (B).
With a high-moisture permeability thin film layer (A) side
(O), wherein the high moisture permeability thin film layer (A) and the low moisture permeability thin film layer (B) have a temperature of 40 ° C based on JIS Z0208.
° C., a moisture permeability at a relative humidity of ^{90% RH (g / m 2} · 24hr)
Are Pa and Pb, respectively, where Pa ≧ 300 (1) Pb ≧ 100 (2) Pa ≧ 3 × Pb (3) Easy-to-adhere laminating film. 2. The gas permeability of the high-moisture vapor-permeable thin film layer (A) is determined by measuring the oxygen permeability (measured according to ASTM D-1434-75) at 30 cc / 24.
The easy-to-adhere laminating film according to claim 1, which is not more than hr · m ² · atm. 3. The laminated film according to claim 1, which is a film to be attached to the target surface (O) with water. 4. The laminated film according to claim 1, wherein the high moisture-permeable thin film layer (A) and / or the low moisture-permeable thin film layer (B) are blended with a function-imparting substance. 5. A laminating film obtained by laminating the laminating film according to claim 1 on the target surface (O) such that the high-moisture-permeable thin film layer (A) side is the target surface (O). Kimono. 6. The adhesive product according to claim 5, wherein the target surface (O) is a glass surface.