JP2692189B2 - Composite film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite film. More specifically, the present invention relates to a composite film having excellent adhesion to a metal vapor deposition layer.

[Prior Art] Metal evaporated films are used for various purposes. However, in general, the metal vapor deposition film has a weak adhesion between the substrate film and the metal vapor deposition layer, and not only becomes inferior particularly in a high humidity environment, but also the disappearance of the metal vapor deposition layer becomes remarkable. Furthermore, in applications such as laminating a metallized film with a sealand layer, the adhesion between the base film and the metallized layer is weak, which is known to cause various problems in post-processing or the properties of the final product. ing. For this reason, various studies have heretofore been made to improve the adhesion of the metal vapor deposition layer. As such a composite film, (1) after performing corona discharge treatment or the like on the base film,
Composite film with metal deposition.

(2) A composite film in which metal is vapor-deposited on a base film and then heat-treated.

(3) A composite film obtained by coating an easily adhesive resin, an organic silane compound, or an organic titanium compound on a base film and then vapor-depositing a metal, for example, JP-A-59-79732 and JP-A-5-79732.
There is a publication such as 6-112453.

Etc. are known.

[Problems to be Solved by the Invention] However, the above-mentioned composite film has the following problems. That is, although an improvement in the adhesive force between the base film and the metal vapor deposition layer is recognized, the improvement effect is small and not sufficiently satisfactory. Furthermore, the adhesion of the metal vapor deposition layer in a high humidity atmosphere hardly improves.

The present invention solves these drawbacks of the prior art, and provides a composite film having excellent adhesion to a metal vapor deposition layer and excellent water resistance and moisture resistance of the metal vapor deposition layer.

[Means for Solving the Problems] According to the present invention, a coating layer containing an oxyketone complex salt compound as a main component is coated on at least one surface of a substrate film, and a metal vapor deposition layer is further provided on the coating layer. The gist of the invention is the characteristic composite film.

The base film in the present invention is not particularly limited in its composition, but is preferably a film made of a resin selected from thermoplastic resins, thermosetting resins and the like. Specific examples of the resin include polyester, polyolefin, cellulose acetate, polyvinyl chloride, polyimide, polycarbon, polyimide amide, polyphenylene sulfide, and the like. However, a thermoplastic resin is preferable because melt extrusion film formation is possible. Further, the resin may be blended or copolymerized with another type of polymer within a range not impairing the object of the present invention,
Known additives such as heat stabilizers, oxidation stabilizers, weather stabilizers, UV absorbers, pigment dyes, organic or inorganic fine particles, organic lubricants, fillers, release agents, antistatic agents, etc. are blended. May be.

Furthermore, polyester is preferable for various reasons such as mechanical strength, rigidity, dimensional stability, and heat resistance of the film. Examples of the polyester include those mainly composed of saturated linear polyester, and include polyethylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate, polyethylene-p-oxybenzoate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene bis-α. , Β-bis2-chlorophenoxyethane-4,
Typical examples are 4'-dicarboxylate and its derivatives. Furthermore, among the polyesters, polyethylene terephthalate is most preferable because it has a good overall balance of the physical properties of the film and that the raw materials are easily available at low cost.

The coating layer in the present invention is a layer containing at least one oxyketone complex salt compound as a main component. The main component means that the content of the main component is 50% or more, preferably 60% or more, more preferably 70% or more in the coating layer, and may appropriately contain other substances. In the present invention, such a coating layer is provided on at least one side of the substrate film. However, in the case where it is provided on both sides, the following description applies to at least one side.

The oxyketone complex salt compound in the present invention is a kind of organometallic coordination compound, and representative compounds are described in "Large Organic Chemistry Vol. 18" (published by Asakura Shoten Co., Ltd.), for example, acetylacetone complex salt, Examples thereof include theonyltrifluoroacetone complex salt, dibenzoylmethane complex salt, α-benzoinoxime complex salt, 0-oxyacetophenone complex salt, 1-oxyxanthone complex salt, and pyromecon complex salt. Among them, the adhesion to the base substrate and the composite film Acetylacetone complex salts are particularly preferable in terms of properties and the like. Acetylacetone complex salt takes the form of monoacetylacetone complex salt, zesacetylacetone complex salt, trisacetylacetone complex salt, tetrakisacetylacetone complex salt, etc., depending on the valence and coordination number of the metal forming the complex salt, and the type of metal forming the complex salt is, for example, lithium, Sodium, potassium, silver, titanium, gold, gallium, cobalt, antimony, tin, iron, copper, beryllium, nickel, barium,
Examples thereof include calcium, zinc, magnesium, manganese, aluminum, boron, indium, and cesium. Among them, aluminum, copper, tin, iron, and silver are preferable because of the characteristics of the composite film.

The substrate film constituting the film of the present invention is not particularly limited in its orientation state, and may be non-oriented, uniaxially oriented, or biaxially oriented, but is biaxially oriented in terms of mechanical strength, dimensional stability and rigidity. The thing of a state is desirable. Although the thickness of the substrate film is not particularly limited, it is preferably 1 to 500 μm, more preferably 5 to 300 μm, and excellent in handleability in practical use as a substrate base. The surface roughness and optical haze of the base film are not particularly limited and may be desired depending on the application.

The laminated thickness of the coating layer constituting the film of the present invention is not particularly limited, but is preferably 0.001 to 3.0 μm,
The thickness in the range of 0.01 to 1.0 μm is desirable from the viewpoints of uniform formation of the coating layer and adhesion. Further, the coating layer, the adhesion of the oxyketone complex salt compound, water resistance, solvent resistance, an organic polymer resin for improving the mechanical strength, a cross-linking material, an epoxy compound as a known adhesion promoter, an aziridine compound,
A reactive compound such as a blocked polyisocyanate or a vinyl compound may be contained. Further, if necessary, known additives such as antifoaming agents, coating improvers, thickeners, antistatic agents, dyes, pigments, etc. in amounts that do not impair the effects of the present invention.
A lubricant or the like may be included.

The metal vapor deposition layer referred to in the present invention, aluminum, zinc, copper, low melting point metal such as tin by a known vacuum vapor deposition method, an oxide thereof, or an alloy containing them, further Fe, Co,
It is a layer formed by adhering Ni or other ferromagnetic metals or magnetic alloys containing them to the base film. Also,
The metal deposition layer may be in the form of a composite layer of different metals. The thickness of the metal vapor deposition layer is not particularly limited and is 0.02 to 0.2 μm.
A range of degrees is preferred.

Next, the manufacturing method of the present invention will be described. However,
It is not limited to this.

First, the base film of the present invention is obtained, for example, by melt-extruding the above-mentioned thermoplastic resin from a die by an extruder, casting it into a sheet, and stretching it by a known method, if necessary. The stretching method is not particularly limited, but biaxial stretching is preferably carried out, for example, by simultaneous biaxial vertical-horizontal, vertical-horizontal-vertical, horizontal-vertical, and two-stage vertical-horizontal stretching.

Next, a coating layer composed of a composition containing at least one oxyketone complex salt compound as a main component is provided on at least one surface of the base film. As a method for providing the coating layer, a solution of the above composition prepared in a predetermined amount is applied to an unstretched film serving as a substrate, the coating film is dried, and then biaxially stretched sequentially or simultaneously.

A method in which an unstretched film to be a substrate is stretched in one direction in advance, a solution of the composition prepared in a predetermined amount is applied, the coating film is dried, and then stretched in a direction perpendicular to the initial stretching direction. .

The base film is biaxially stretched in advance,
Next, a method of applying a solution prepared in a predetermined amount, and then drying.

Etc. are preferably applicable, but are preferable in terms of stability and productivity. These methods are generally carried out by the end of the base film forming process, but a method of providing a coating-drying process after once winding the base film as a single film may be used. Furthermore, after the above-mentioned operation of the substrate,
For example, a process such as re-stretching may be added. The solution of the composition to be applied can be used in the form of a water-soluble or aqueous dispersion, an aqueous emulsion, or an organic solvent solution.

The application method is not particularly limited, and an extrusion lamination method, a melt coating method, or the like may be used, but a gravure coating method, a reverse coating method, a kiss coating method, a die coating method, because a thin film can be coated at a high speed. A known method such as a metaling bar coating method can be applied. In addition, by performing a known surface treatment such as a corona discharge treatment in air or other various atmospheres as necessary before coating, not only the coating properties are improved,
The coating layer can be more firmly formed on the surface of the base film.
The coating material concentration and the coating film drying conditions are not particularly limited, but it is desirable that the coating film drying conditions be performed within a range that does not adversely affect various properties of the coating layer and the base film.

Then, a metal vapor deposition layer is formed on the base film provided with the coating layer by a known vacuum vapor deposition method. At this time, the coating layer may be subjected to known surface treatment such as corona discharge treatment, if necessary.

[Evaluation Method] The characteristic value of the present invention is based on the following measuring method and evaluation criteria.

(1) Adhesion of metal vapor deposition layer Cellophane tape: CT-24 (manufactured by Nichiban Co., Ltd.) was attached to the metal vapor deposition layer provided on the coating layer of the composite film, and a load of about 5 kg was applied using a hand roller, Length direction (about 10m
After being reciprocated 10 times to m) and pressure-bonded, the cellophane tape was peeled by hand to observe and evaluate the degree of peeling of the metal vapor deposition layer. The criterion for judgment is that the peeled area is less than 5% (good), the peeled area is 5
% Or more was regarded as defective (x).

(2) Water resistance (wetness) of metal vapor deposition layer Water was placed in a constant temperature bath and heated to 65 ° C, and the metal vapor deposition film was immersed in this for 15 minutes, and the degree of disappearance of the vapor deposition film was observed. The evaluation criteria were evaluated by three levels of resistance to hot water, with ◯ when the vapor deposition film did not change, Δ when slightly changed, and x when the vapor deposition film almost disappeared.

[Advantages of the Invention] (1) The composite film has excellent adhesion to the metal vapor deposition layer.

(2) The metal vapor deposition layer provided on the composite film is water resistant,
Since it has excellent moisture resistance, it maintains sufficient adhesion even in a high humidity environment.

(3) Since the metal vapor deposition layer provided on the composite film has excellent adhesion, it has excellent handleability in post-processing.

The composite film of the present invention can be widely applied to base films for capacitors, packaging base films, magnetic recording medium base films, various photographic base films, optical base films, graphic base films, and the like.

EXAMPLES The present invention will be described with reference to the following Examples and Comparative Examples.
The present invention is not limited to these.

Example 1 A homopolymer chip of polyethylene terephthalate (intrinsic viscosity: 0.62, melting point: 259 ° C.) manufactured by a conventional method was mixed with 1
It was dried under reduced pressure (3 mmHg) at 80 ° C. for 2 hours. This chip 280
Feed to extruder with screw with compression ratio of 3.8 at T
Melt extrusion from mold die, surface temperature of 20 using electrostatic imprinting
The film was wound around a cooling drum at ℃ and solidified by cooling to give an unstretched film, and the film thus obtained was stretched by a factor of 3.3 in the machine direction by roll stretching at 90 ° C, and the coated surface was subjected to corona discharge treatment. Next, a coating material having a concentration of 2.0% by weight in which acetylacetone aluminum was uniformly dissolved in isopropyl alcohol as an oxyketone complex salt compound was applied to one surface of the uniaxially stretched film by a metalling bar method, and then the coating layer was dried to 100%. Stretched 3.6 times in the transverse direction at ℃, 2 in the transverse direction
Heat treatment was carried out for 10 seconds at 210 ° C. while being% relaxed to obtain a composite film having a thickness of 30 μm. The thus-obtained composite film was vacuum-deposited with aluminum on the coating layer at a pressure of 10 ⁻⁴ Torr using a winding-type vacuum vapor deposition machine. The vapor deposition layer thickness was 0.06 μm. The characteristics of this vapor-deposited film are as shown in Table 1, and the vapor-deposited layer had excellent adhesion and water resistance.

Example 2 After a corona discharge treatment was applied to the surface of a biaxially oriented polyphenylene sulfide film having a thickness of 25 μm, the same coating material as in Example 1 was applied by a metering bar method to form a coating layer of 130.
A composite film was obtained by drying at 3 ° C. for 3 minutes. Next, aluminum was vacuum-deposited on the coating layer of the obtained composite film in the same manner as in Example 1. The vapor deposition layer thickness was 0.06 μm, and the characteristics of this vapor deposition film are shown in Table 1. As can be seen from Table 1, both the adhesion and the water resistance of the vapor deposition layer are excellent.

Example 3 A surface of a biaxially oriented polyethylene terephthalate film having a thickness of 38 μm was subjected to corona discharge treatment, and then a coating material having a concentration of 3.0% by weight, in which acetylacetone copper as an oxyketone complex salt compound was uniformly dissolved in chloroform, was applied by a metaling bar method. And the coated layer was dried at 130 ° C. for 2 minutes to obtain a composite film. Next, aluminum was vacuum-deposited on the coating layer of the composite film in the same manner as in Example 1. The thickness of the vapor-deposited layer was 0.06 μm. The properties of this vapor-deposited film were as shown in Table 1, and the adhesion and water resistance of the vapor-deposited layer were excellent.

Example 4 Based on Example 3, a composite film was obtained in the same manner as in Example 3 except that a coating material having a concentration of 3.0 wt% in which iron acetylacetone was uniformly dissolved in chloroform was used as the oxyketone complex salt compound. Aluminum was vacuum-deposited in the same manner. The thickness of the vapor-deposited layer was 0.06 μm, and the characteristics of this vapor-deposited film were that the vapor-deposited layer had excellent adhesion and water resistance as shown in Table 1.

Example 5 Based on Example 3, a composite film was obtained in the same manner as in Example 3 except that a coating material having a concentration of 1.0% by weight in which iron dibenzoylmethane was uniformly dissolved in chloroform was used as an oxyketone complex salt compound. . Thereafter, aluminum was vacuum-deposited in the same manner. The thickness of the deposited layer is 0.06 μm. The properties of the vapor deposited film are shown in Table 1. The vapor deposition layer had excellent adhesion and water resistance.

Comparative Example 1 The same raw material chip as in Example 1 was used, and an organic titanium compound "Organix" TC-310 (manufactured by Mammoto Trading Co., Ltd.) as a coating material was uniformly dissolved in water to have a concentration of 3.0% by weight. A composite film was obtained in the same manner as in Example 1 except that the above was used. Next, aluminum was vacuum-deposited on the coating layer of the composite film in the same manner as in Example 1. Deposition layer thickness is 0.06μ
The characteristics of this vapor-deposited film were as shown in Table 1, and the vapor-deposited layer was inferior in water resistance.

Comparative Example 2 After a corona discharge treatment was applied to the surface of a biaxially oriented polyethylene terephthalate film having a thickness of 25 μm, aluminum was vacuum-deposited on the surface by the same method as in Example 1.
The vapor deposition layer thickness was 0.06 μm. As shown in Table 1, the vapor-deposited film had poor water resistance of the vapor-deposited layer.

Claims (1)

(57) [Claims] 1. A composite film comprising a base film, a coating layer comprising an oxyketone complex salt compound as a main component, which is coated on at least one side, and a metal vapor deposition layer provided on the coating layer.