JPH08318609A - Laminate with iris pattern and glass film - Google Patents

Abstract

(57) [Summary] [Purpose] To improve the drawbacks of the iris development technology used for glass pasting films up to now, to provide a laminate having an arbitrary and beautiful iris pattern, and a glass pasting film exhibiting an iris pattern. The purpose is to obtain. [Structure] A laminate comprising an iris thin film layer provided on a transparent molded body, the iris thin film layer having a visible light transmittance of 1
Semi-transparent metal thin film layer A of 0 to 70%, transparent resin thin film layer B
And a semitransparent thin film layer C having a visible light transmittance of 20 to 90%. [Effect] Mainly used as a film for attaching glass.
By adjusting the thickness of the transparent resin thin film layer, it is possible to mass-produce a laminate having an iris pattern with an arbitrary pattern. A transparent molded body, a transparent resin thin film layer, a semitransparent thin film layer, a dye,
By mixing the pigment, it is possible to obtain a laminate having a colorful and beautiful iris pattern in which coloring and iris are woven.
By mixing fine bubbles in a transparent molded body, a transparent resin thin film layer, or a semitransparent thin film layer, a laminate having a variety of beautiful iris patterns woven by light scattering and iris can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having an iris color pattern. More specifically, the present invention relates to a laminate having an iris pattern which is suitable for use mainly in a film for glass application. .

[0002]

2. Description of the Related Art Conventionally, many proposals have been made as a laminate having an iris pattern on its surface, which are exemplified by the following (a) to (c).

(A) Zinc sulfide, titanium oxide, tin oxide,
Laminate by the method of double-layer vapor deposition of special compounds such as magnesium fluoride and copper iodide.

(B) A laminate having a titanium oxide thin film layer as described in JP-B-37-8731.

(C) A thin metal layer, a transparent varnish, and another metal layer laminated on a plastic film as described in JP-B-45-39958, and JP-B-51-33589. Such as a light-reflecting film, an interference resin film, and a translucent metal film, and Japanese Patent Publication No.
A laminated body exhibiting an iris pattern in which an interference resin film having a light-reflecting film unevenness and a semitransparent metal film are laminated as in JP-A 2-1413.

However, these conventional laminates and their manufacturing methods have their respective drawbacks when used for a glass laminating film. For example, in the laminated body produced by the above method (a), the laminated materials are special, and it is necessary to vapor-deposit these materials to have an optical thickness of about 1000 angstroms or more, which is not suitable for mass production, and the obtained iris can be obtained. It is difficult to adjust the pattern of to any pattern.

In the laminated body of (b), since hydrochloric acid gas is generated because titanium tetrachloride gas is used, there are problems such as corrosion of manufacturing equipment and environmental problems.

Further, in the case of the laminated body of (c), since it is a metal vapor deposition or a metal foil centering on aluminum or the like as the light reflecting film, it is an opaque film having a transmittance of 1% or less, and therefore opaque. It becomes a laminated body with a nice iris pattern.
When these are attached to various objects to be decorated, the appearance of the surface is blocked by the opaque iris pattern. For this reason, there is a drawback in that the outside of the glass cannot be seen when it is pasted onto the glass, and it cannot be applied as a film for pasting glass.

[0009]

DISCLOSURE OF THE INVENTION The present invention aims to improve the above-mentioned drawbacks of the iris developing technique used for the conventional glass laminating film, and to obtain a laminate having an arbitrary colorful and beautiful iris pattern. It is intended.

[0010]

According to the present invention, in a laminate comprising an iris thin film layer provided on a transparent molded body, the iris thin film layer comprises a semitransparent metal thin film layer A and a transparent resin thin film layer. B and a semitransparent thin film layer C, and the visible light transmittance of the semitransparent metal thin film layer A is preferably 10 to 70%, and the visible light transmittance of the semitransparent thin film layer C is preferably 10% to 70%. It is preferable to provide a laminate having an iris pattern characterized by being 20 to 90%.

A laminated body having an iris pattern according to the present invention will be described below with reference to FIGS. 1 and 2.

Here, the stacking order of the thin films in the iris thin film layer is that of FIG. 1 in the order of A / B / C, and that of FIG. 2 in the order of C / B / A. Needless to say, the present invention is not limited to the description below.

The transparent molded article 1 in the present invention includes film-shaped, sheet-shaped, plate-shaped and block-shaped molded articles such as synthetic resin, paper and glass.

The transparent molded body 1 may be a colored transparent body or a colorless transparent body. In the case of a colored transparent molded product, since the layer for imparting an iris pattern laminated thereon has a semi-transparent iris color, a laminate having a semi-transparent colored iris pattern fused with the coloring of the molded product. Become. Further, in the case of a transparent molded body, the layer for imparting an iris pattern laminated thereon has a semitransparent iris color, so that the layered product has a translucent and beautiful iris pattern as a whole.

The transparent molded article 1 is preferably a sheet-like material having plasticity in terms of easiness of imparting an iris pattern to the surface and productivity. Among them, synthetic resin film,
For example, polyethylene terephthalate, polyester typified by polybutylene terephthalate, polyolefin typified by polyethylene, polypropylene, polyamide typified by nylon 6, nylon 66 and nylon 12, polynitrocellulose, typified by polycellulose acetate. Cellulosic, polyvinyl alcohol,
Specific examples include films made of organic resins such as polyethylene trifluoride, polycarbonate, polymethylmethacrylate, polyimide, vinyl chloride, vinylidene chloride, etc. This is a single layer and two or more sheets are laminated together. It may be Further, those whose surface has been subjected to mat processing, hairline processing, spin processing or the like in advance can also be used.

Although the thickness of the transparent molded body 1 varies depending on the use, etc., it is usually about 12 to about 100 microns, and regarding the transparency, the visible light transmittance is usually 70% or more. belongs to.

In the present invention, this transparent molded article,
An undercoat layer may be further provided between the semi-transparent iris thin film layer. This undercoat layer is provided for improving adhesion, abrasion resistance, antistatic property, water resistance, chemical resistance, etc.,
A film thickness of about 0.005 to about 5 microns is preferred.

The subbing layer in the present invention is exemplified by the following (d) and (e), and is a transparent thin film layer.

(D) A polyester resin, an acrylic resin, a urethane resin, a melamine resin, an epoxy resin or the like is used alone or in a mixture by various known methods such as a gravure coating method and a bar roll coating method, and a curing agent is added if necessary. Thin film obtained by addition.

(E) Resistance heating method or high frequency heating vapor deposition method, sputtering method, ion plating method, etc.
A known method such as so-called vacuum vapor deposition method, chemical vapor deposition method, or wet plating method, which is made transparent by a grading method of metals such as Al, Ni, Cu, Fe, or Al ₂ O ₃ , S
A thin film obtained by coating a metal compound such as iO alone or in combination.

The iris thin film layer 2 in the present invention is composed of three layers, a semitransparent metal thin film layer A, a transparent resin thin film layer B, and a semitransparent thin film layer C.

The semitransparent metal thin film layer A of the present invention is, for example,
A known method such as a resistance heating method or a high-frequency heating evaporation method, a sputtering method, an ion plating method, a so-called vacuum evaporation method, a chemical vapor deposition method, a wet plating method, or the like is used.
It is an uncolored or colored semitransparent metal thin film layer which can be obtained by coating a metal such as 1, Ni, Cu, Fe or the like or a mixture thereof and has a visible light transmittance of preferably 10 to 70%.

In the present invention, the semi-transparent metal thin film layer A made of a metal is formed by a transparent heating method such as a resistance heating method, a high frequency heating evaporation method, a sputtering method, an ion plating method, a so-called vacuum evaporation method or a chemical vapor deposition method. 1 can be thinly vapor-deposited and laminated. The film thickness is usually about 50 to 300 angstroms.

Next, the transparent resin thin film layer B in the present invention
Is exemplified by (f) to (h) below, and is an uncolored or colored transparent resin thin film layer B.

(F) A thermoplastic resin such as a copolymer of vinylidene chloride and vinyl chloride, vinyl acetate, vinyl alcohol or the like, or a copolymer of polyvinyl chloride, polyvinylidene chloride or polystyrene and vinyl chloride or styrene. And a thin film layer having fine bubbles formed by a gas generated by decomposing the above organic material by various methods such as light and heat.

(G) Polystyrene, polycarbonate, melamine resin, phenol resin, vinyl copolymers including acrylics, fibrin copolymers, urethane copolymers and various curing agents for curing them, curable functional groups A thin film layer made of a composition having a group, a thin film layer made of an organically substituted silicon compound, and a thin film layer made of the above organic material and inorganic fine particles such as titanium oxide, aluminum oxide and zirconium oxide.

(H) Titanium tetraethoxide, titanium tetra-n-propoxide, aluminum ethoxide,
A metal alcoholate compound such as zirconium tetra-n-butoxide, a chelate compound such as di-isopropoxytitanium bisacetylacetonate and tri-n-butoxide zirconium monoethylacetoacetate, and further zirconyl ammonium carbonate or zirconium as a main component. A liquid film-forming inorganic material such as an active inorganic polymer, or a mixture of the above-mentioned inorganic material and an alkyl silicate or a hydrolyzate thereof, colloidal silica sol, an acrylic-containing vinyl-based copolymer, and fluorine substitution Film layer made of a mixture of the above-mentioned materials with various organic polymers, aromatic ring-free polyester polymers, silicone polymers and the like.

The transparent resin thin film layer B may be a coating film having a uniform thickness or a nonuniform thickness. The thickness range is particularly preferably in the range of 100 to 10,000 angstroms. In the case of uneven thickness, it is preferable that the difference in thickness between the concave portion and the convex portion is about 200 to 2000 angstrom in order to obtain a beautiful iris pattern. It is not necessarily limited to this range.

The transparent resin thin film layer B can be applied by a general resin coating method such as roll coating or gravure coating, a printing method or a spraying method.

When a metal compound thin film layer is used instead of the transparent resin thin film layer B, the processing method is so-called vacuum vapor deposition method such as resistance heating method or high frequency heating vapor deposition, sputtering method, ion plating method and chemical vapor deposition method, It is a known method such as a wet plating method. In this case, since it is difficult to change the thickness of the metal compound thin film layer and the variety of the patterns, in the iris using the metal compound thin film layer instead of the transparent resin thin film layer B, it is difficult to reproduce the iris color and the variety of the patterns is different. Sex can be difficult. In addition, when a metal compound thin film layer is used in place of the transparent resin thin film layer B, the transparency is lowered and the brightness of the iris color is sometimes lowered.

The resin thin film layer B is not limited to those made of the above-mentioned various materials, but the semi-transparent thin film layer C.
If the difference in the refractive index is 0.05 or more, it is not limited to these. When the difference in refractive index between the resin thin film layer B and the thin film layer C is less than 0.05, the iris pattern tends to become unclear. In the present invention, the resin thin film layer B is not necessarily made of a single substance, and may be a mixture of two or more substances. Further, two or more layers of different substances may be laminated if there is a difference of 0.05 or more from the refractive index of the thin film layer C. Regarding transparency, the visible light transmittance is usually 90% or more.

The semitransparent thin film layer C in the present invention is exemplified by the following (i) to (m).

(I) Al, Ni, Cu, Fe, etc. by known methods such as so-called vacuum evaporation method such as resistance heating method or high frequency heating evaporation method, sputtering method, ion plating method and chemical vapor deposition method, wet plating method, etc. A thin film obtained by coating the above metals alone or in combination.

(J) Titanium oxide, silicon oxide, zinc oxide, antimony oxide, zinc sulfide, magnesium fluoride,
A thin film layer of a metal compound such as potassium fluoride or cryolite.

(K) Copolymer of vinylidene chloride and vinyl chloride, vinyl acetate, vinyl alcohol, etc., or thermoplastic resin such as copolymer of polyvinyl chloride, polyvinylidene chloride, polystyrene and vinyl chloride, styrene, etc. And a thin film layer having fine bubbles formed by a gas generated by decomposing the above organic material by various methods such as light and heat.

(L) Polystyrene, polycarbonate, melamine resin, phenol resin, vinyl copolymers including acrylics, fibrin copolymers, urethane copolymers and various curing agents for curing them, curable functional groups A thin film layer made of a composition having a group, a thin film layer made of an organically substituted silicon compound, and a thin film layer made of the above organic material and inorganic fine particles such as titanium oxide, aluminum oxide and zirconium oxide.

(M) Titanium tetraethoxide, titanium tetra-n-propoxide, aluminum ethoxide,
A metal alcoholate compound such as zirconium tetra-n-butoxide, a chelate compound such as di-isopropoxytitanium bisacetylacetonate and tri-n-butoxide zirconium monoethylacetoacetate, and further zirconyl ammonium carbonate or zirconium as a main component. A liquid film-forming inorganic material such as an active inorganic polymer, or a mixture of the above-mentioned inorganic material and an alkyl silicate or a hydrolyzate thereof, colloidal silica sol, an acrylic-containing vinyl-based copolymer, and fluorine substitution Film layer made of a mixture of the above-mentioned materials with various organic polymers, aromatic ring-free polyester polymers, silicone polymers and the like.

The semitransparent thin film layer C composed of the above (i) and (j) is formed of a transparent resin by a so-called vacuum vapor deposition method such as resistance heating method or high frequency heating vapor deposition method, sputtering method, ion plating method and chemical vapor deposition method. The thin film layer B is thinly vapor-deposited and laminated.

The semitransparent thin film layer C composed of the above (k) to (m) is a transparent resin thin film layer B formed by a general resin coating method such as roll coating or gravure coating, or a printing method or a spray method. Apply thinly on top and stack.

The visible light transmittance of the semitransparent thin film layer C used in the present invention is preferably 20 to 90%, more preferably 30 to 90%, which is an uncolored or colored semitransparent thin film layer.

The semi-transparent thin film layer C is not limited to the ones made of the above-mentioned various materials, and is not limited thereto as long as the difference in refractive index from the resin thin film layer B is 0.05 or more. When the difference in refractive index between the semitransparent thin film layer C and the resin thin film layer B is less than 0.05, the iris pattern tends to be unclear. The semitransparent thin film layer C does not necessarily have to be made of a single substance, and may be a mixture of two or more substances. Further, two or more layers of different substances may be laminated if there is a difference of 0.05 or more from the refractive index of the resin thin film layer B.

The iris thin film layer 2 is used depending on the purpose of use.
A protective layer may be provided on the top surface to improve water resistance and the like. In addition, an adhesive layer may be provided in order to laminate the laminate having such an iris pattern with other molded products.

The visible light transmittance of the semitransparent metal thin film layer A in the present invention is preferably 10 to 70%, and the semitransparent thin film layer C is preferably.
The visible light transmittance of is preferably 20 to 90%. The visible light transmittance of the semitransparent metal thin film layer A is 10%.
If it is below, the transmittance of the entire iris thin film layer will be lowered, and the outside of the glass will be difficult to see when it is pasted on glass, which may cause a drawback that it cannot be applied as a film for pasting glass. The visible light transmittance of the semitransparent thin film layer C is 20%.
If it is less than the above, the transmittance of the entire iris thin film layer will be lowered, and the outside of the glass will be difficult to see when it is pasted on glass, which may cause a drawback that it cannot be applied as a film for pasting glass. The visible light transmittance of the semitransparent metal thin film layer A is 70%.
As described above, when the visible light transmittance of the semitransparent thin film layer C is 90%, the light transmittance may be too high and a beautiful iris pattern may not be exhibited.

In FIG. 1, the visible light transmittance of the semitransparent metal thin film layer A in the present invention is preferably 10 to 70%, and the visible light transmittance of the semitransparent thin film layer C is preferably 20 to 90%. When viewed from the semi-transparent thin film layer C side, the iris color is colorful and looks beautiful. On the other hand, when viewed from the semitransparent metal thin film layer A side in FIG. 1, the iris color appears light due to the metallic luster of the semitransparent metal thin film layer A. Further, in FIG. 1, if an adhesive layer is provided on the side of the semitransparent thin film layer C and the film is attached to the inside of the window of the automobile, a colorful and beautiful iris color can be seen from the outside of the automobile to give the appearance of a fashionable automobile. In the car (driver)
From a closer look, the iris color appears thin and there is little obstacle to driving. When the molded body is colored, the metallic luster of the semitransparent metal thin film layer A is reduced, and the hindrance in operation is further reduced.

Next, the present invention will be described in detail with reference to examples.

[0046]

【Example】

(Example 1) A biaxially stretched polyethylene phthalate film with a visible light transmittance of 87% having a thickness of 25 μ (refractive index 1.6
On one surface of 5), a 10% concentration methyl ethyl ketone solution of polyester resin (refractive index 1.65) was applied by a # 3 bar coater and dried at 120 ° C. to form an undercoat layer having a thickness of about 0.5 μm. .

Moreover, using a bell jar type vapor deposition machine,
The aluminum was vacuum deposited at × 10 vacuum degree ^-2 Pascal. The deposited aluminum had a thickness of 200 Å, and the vapor deposition film obtained had a visible light transmittance of 35%. 10% of nitrocellulose (refractive index 1.51) on the aluminum thin film layer of polyethylene terephthalate film laminated with this aluminum
The methyl ethyl ketone solution having a concentration was applied non-uniformly in a horizontal pattern by moving a # 8 bar coater intermittently at a cycle of about 3 cm, and dried in a hot air circulation oven at 150 ° C. for 30 seconds.

The obtained laminated polyethylene terephthalate film had a beautiful transparent iris pattern with a bluish lateral pattern. However, if you stick a transparent adhesive tape on the nitrocellulose coated surface of this film,
The iris pattern has disappeared. The iris pattern became the original iris pattern by peeling off the adhesive tape.

Further, from above the nitrocellulose coating film on the side of one area layer of the iris pattern film, in a bell jar type vapor deposition machine in a vacuum degree of 5 × 10 ^-2 Pascal, an aluminum film of 150 Å was formed in the same manner as above. It was vacuum-deposited so as to have a thickness (visible light transmittance of 50%). The iris pattern of the lateral pattern of the obtained laminated polyethylene terephthalate film became darker and more beautiful. Even when a transparent adhesive tape was attached to the vapor deposition surface of this film, this beautiful iris pattern did not disappear. (Example 2) Biaxially stretched polyethylene phthalate film with a visible light transmittance of 87% having a thickness of 25 μ (refractive index 1.6
On one surface of 5), a 10% concentration methyl ethyl ketone solution of polyester resin (refractive index 1.65) was applied by a # 3 bar coater and dried at 120 ° C. to form an undercoat layer having a thickness of about 0.5 μm. .

In addition, using a bell jar type vapor deposition machine,
Aluminum was vacuum deposited in a vacuum of 5 × 10 ^-2 Pascal. The deposited aluminum had a thickness of 150 Å, and the vapor deposition film obtained had a visible light transmittance of 50%.

A 10% methylethylketone solution of nitrocellulose (refractive index 1.51) was placed on the aluminum thin film layer of the polyethylene terephthalate film laminated with this aluminum, and a # 8 bar coater was used for about 3 times.
By intermittently moving in a cm cycle, it is applied unevenly in a horizontal pattern, and then 3 in a hot air circulation oven at 150 ° C.
It was dried for 0 seconds. The obtained laminated polyethylene terephthalate film had a beautiful transparent iris pattern with a bluish lateral pattern. However, when a transparent adhesive tape was applied to the nitrocellulose coated surface of this film, the iris pattern disappeared. The iris pattern became the original iris pattern by peeling off the adhesive tape.

Further, zinc sulfide was added to the nitrocellulose coating film on one side of the iris pattern film side in a bell jar type vapor deposition machine at a vacuum degree of 5 × 10 ^-2 Pascal to 400 wt.
It was vacuum-deposited so as to have a thickness of angstrom. The lateral iris pattern of the obtained laminated polyethylene terephthalate film became more dark and beautiful. Even when a transparent adhesive tape was attached to the vapor deposition surface of this film, this beautiful iris pattern did not disappear. (Example 3) A 10% concentration methyl ethyl ketone solution of a polyester resin (refractive index 1.65) was applied by a gravure coating method to one side of a biaxially stretched polyethylene terephthalate film having a thickness of 18 μm and a width of 1 m, and dried at 120 ° C. To form an undercoat layer having a thickness of about 0.5 μm.

Aluminum was vacuum-deposited on the undercoat layer using a bell jar type vapor deposition machine in a vacuum degree of 5 × 10 ^-2 Pascal. The thickness of the attached aluminum is 1
At 50 Å, the resulting vapor-deposited film had a visible light transmittance of 50%. Nitrocellulose (having a refractive index of 1.5 is formed on the aluminum thin film layer of the polyethylene terephthalate film in which the aluminum is laminated).
1) 95 g, epoxy resin (refractive index 1.55) 5.5 g
Of 10% methyl ethyl ketone solution of No. 2 was applied by the gravure coating method, dried at 150 ° C. for 30 seconds, and then 200-2000.
An uneven film of Angstrom was obtained. The obtained laminated polyethylene terephthalate film had a beautiful transparent iris pattern having colors of blue to red.

The following paint A was applied from the nitrocellulose epoxy coating film on the one-sided layer side of the above iris pattern film by the gravure coating method to obtain a 400 angstrom thin film, and a transparent and beautiful iris pattern with higher brightness was obtained. It became a laminated body exhibiting.

Paint A: To 162 g of acetylacetone, 32.2 g of tetra-n-butyl titanate, 10 g of methanol-dispersed colloidal silica and 0.11 g of a silicone surfactant were added and mixed under stirring.

[0056]

EFFECTS OF THE INVENTION The iris-patterned laminate according to the present invention is mainly used as a glass-pasting film for vehicles such as automobiles, yarns, packaging materials, wallpaper, posters, labels and women, making use of its beautiful appearance characteristics. Used for clothing, belts and fishing rods, buttons, earrings, pendants, etc. Further, the present invention has the following effects (n) to (p).

(N) By adjusting the thickness of the transparent resin thin film layer B, a laminate having an iris pattern having an arbitrary design can be mass-produced.

(O) A transparent molded product, a transparent resin thin film layer B, and a semitransparent thin film layer C are mixed with dyes and pigments to obtain a laminate having a colorful and beautiful iris pattern woven by coloring and iris. be able to.

(P) By incorporating fine bubbles into the transparent molded body, the transparent resin thin film layer B, and the semitransparent thin film layer C,
It is possible to obtain a laminate having a colorful and beautiful iris pattern, which weaves light scattering and iris.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view showing an embodiment of a laminated body having an iris pattern according to the present invention, in which the order of laminating each thin film layer is A
The iris thin film layers are in the order of / B / C.

FIG. 2 is an enlarged cross-sectional view showing an embodiment of a laminate having an iris pattern according to the present invention, in which the stacking order of each thin film layer is C
The iris thin film layers are in the order of / B / A.

[Explanation of symbols]

 1 …… Molded body 2 …… Iris thin film layer A …… Semi-transparent metal thin film layer B …… Transparent resin thin film layer C …… Semi-transparent thin film layer

Claims (8)

[Claims] 1. A laminate comprising an iris thin film layer provided on a transparent molded body, wherein the iris thin film layer comprises a semitransparent metal thin film layer A, a transparent resin thin film layer B, and a semitransparent thin film layer C. A laminated body having an iris pattern, which is characterized by comprising three layers. 2. The iris pattern according to claim 1, wherein the iris thin film layer comprises a semitransparent metal thin film layer A, a transparent resin thin film layer B, and a semitransparent thin film layer C, which are laminated in this order. A laminate that exhibits. 3. The laminate having an iris pattern according to claim 1, wherein the translucent metal thin film layer A has a visible light transmittance of 10 to 70%. 4. The laminate having an iris pattern according to claim 1, 2 or 3, wherein the translucent thin film layer C has a visible light transmittance of 20 to 90%. 5. The iris-patterned laminate according to claim 1, further comprising an undercoat layer between the transparent molded body and the iris thin film layer. 6. The resin thin film layer B and the semitransparent thin film layer C
The difference in the refractive index is 0.05 or more, and the laminate having an iris pattern according to claim 1. 7. A laminate comprising an iris thin film layer provided on a transparent molded body, wherein the iris thin film layer is a semitransparent metal thin film layer A, a transparent resin thin film layer B, and a semitransparent thin film. A glass sticking film having an iris pattern, which comprises three layers, Layer C. 8. A film for adhering glass having an iris pattern according to claim 7, which is used for vehicles.