JPH0466660A - Thin film production and releasing base film used therefor - Google Patents

Abstract

PURPOSE:To easily produce a thin film made of metal having desired thickness in a defect-free state by using a base film where a releasing layer prepared by adding a copper phthalocyanine dye to amino copolymer resin is provided to one surface of a film. CONSTITUTION:A composition prepared by adding copper phthalocyanine dye to amino copolymer resin is applied to one surface of a heat resisting synthetic resin film and dried, by which a releasing layer is provided. A metal, such as Al, or metal oxide of the desired thickness is vapor-deposited onto the above releasing layer surface, by which a thin metallic film layer is formed. This thin metallic film layer is peeled off from the releasing layer surface. As to the additive quantity of the copper phthalocyanine dye, it is necessary to use this dye by >=0.01%, by weight ratio, based on the amount of the amino copolymer resin used. By this method, the extremely thin film made of metal can easily be peeled off from the releasing surface, in the state free from defects and also free from the adhesion of releasing layer residue.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing a metal thin film and a releasable base film used in the production method, which allows extremely thin metal films to be produced with good reproducibility. It provides new technical means.

In addition, the "metal thin film" in the present invention refers to a thin film of a single metal such as Cu, a thin film of an alloy metal such as Ag-Pd, and a thin film of an alloy metal such as Ag-Pd.
Includes thin films of metal oxides such as To (oxides of In, Sn).

[Conventional technology]

As is well known, metal thin films are used in various fields, especially in the field of electronic materials, ITO, which is a transparent conductive film, is used in various fields.
As seen in thin films, there is a need for thinner, more defect-free, and purer metal thin films.

A thin metal film is obtained by depositing a metal thin film of a desired thickness on the negative side of a base film (e.g. polyester film) or substrate (e.g. glass plate) and peeling the metal thin film from the film surface or substrate surface. Metal thin film manufacturing technology has been well known for a long time.

For example, in Japanese Patent Publication No. 51-29502, on one side of a base film such as a polyester film, a polyethylene film, or a water-resistant polyvinyl alcohol film,
Acrylic resin, vinyl chloride-vinyl acetate copolymer resin,
An undercoat layer of melamine resin or the like with a thickness of 0.35 to 1 μm is provided, and Au and A are deposited thereon by vacuum evaporation.
g. By providing a metal vapor deposited layer such as A1 with a thickness of 0.03 to 0.1 μm, a metal foil consisting of a two-layer integrated structure of an undercoat layer and a metal vapor deposited layer is formed, and the metal foil is peeled off. and providing the metal vapor deposition layer on one surface of the base film by a vacuum vapor deposition method,
A top coat layer of the resin with a thickness of 0.35 to 1 μm is provided thereon to form a metal foil consisting of a two-layer integrated structure of a metal vapor deposition layer and a top coat layer, and the metal foil is peeled off. Technical means are disclosed. Furthermore, the publication states that a release agent such as a silicone resin may be applied to the base film prior to undercoating.

For example, Japanese Patent Application Laid-open No. 60-211065 discloses that a metal or a metal compound such as Au or No is deposited on a substrate such as glass to a thickness of 1 to 100 ml by vacuum evaporation, ion blasting, or sputtering. By forming a film to a thickness of 2 μm and peeling off the film to obtain a foil, the pretreatment of the substrate, which is performed to increase the contact force between the film and the substrate, is reduced. A technical means has been disclosed in which a foil is obtained by reducing the adhesive force between the film and the substrate and peeling off only the film after film formation.

[Problem to be solved by the invention]

However, if an attempt is made to obtain a thinner, more defect-free, and more pure metal thin film using the prior art, the following problems arise. That is, as stated in the above-mentioned patent publication, [When attempting to continuously and mechanically peel off a metal foil consisting of a two-layer or three-layer integral structure from a base film, the metal foil often snaps or breaks. 2 column 24-26
The metal thin film and the resin layer (
Even if the undercoat layer, topcoat layer) is an integral structure, it is difficult to peel the integral structure from the base film without defects, and even more so when the thickness is 0.03~ 0°1μm (300~1,00
It is extremely difficult to peel off only a thin metal film from a base film without any defects.

The technical means disclosed in the aforementioned patent publication is
It is obtained by peeling an integral structure of a metal thin film and a resin layer from a base film, and is not a technique for obtaining the metal thin film itself.

However, the technical means disclosed in the above-mentioned published patent publication obtains the metal thin film itself, but its thickness is
``Creating a relatively thick film (1 to 2 μm) (page 2, bottom left column, line 3)1, as described in 1 μm (10,0 μm),
However, an extremely thin metal thin film with a thickness of about 50 mm has not been obtained, and in fact, the results of experiments conducted by the present inventors show that the technique requires minimal pre-treatment of the substrate. 1 μm thick from the substrate by technical means.
Hereinafter, it was impossible to peel off a metal thin film of, for example, 0.1 μm (1,000 people) without any defects.

Currently, technical means being attempted to form a thin metal film with a thickness of about 50 to 5,000 thick on one side of a base film by vapor deposition and peel the metal thin film from the film surface without any defects are as follows: This is a technical means of providing a release layer on one side of the film, and those skilled in the art will find that the metal thin film can be peeled off as easily as possible, and the release layer residue will not adhere to the peeled metal thin film as much as possible. We are working hard to find a release layer.

However, to the best of the inventor's knowledge, the thickness is still approximately 5.
0 people make extremely thin metal films without defects.
Moreover, no mold release layer has appeared that can be easily peeled off without adhering to mold release layer residual fragrance.

The present invention aims to provide a technical means by which a metal thin film having a thickness of about 50 to 5,000 people can be easily peeled off in a defect-free state and without the release layer remaining as much as possible. This is an issue to be addressed.

In order to achieve the above-mentioned technical problem, the present inventor conducted numerous trial-and-error experimental prototypes in search of a release layer material that has as much adhesion to the base film as possible and as little adhesion to the metal thin film as possible. As a result of repeated efforts, we finally found a material that could be called an ideal release layer material and completed the present invention.

[Means to solve the problem]

The above technical problem can be achieved by the present invention as follows.

That is, the present invention uses a releasable base film in which a release layer made of an amino copolymer resin and a copper phthalocyanine dye is provided on one side of a heat-resistant synthetic resin film, and a metal is applied to the surface of the release layer. Or, a method for producing a metal thin film, which comprises forming a metal thin film layer by vapor-depositing a metal oxide, and then obtaining a metal thin film by peeling the metal thin film layer from the surface of the mold release layer, and the method for producing the metal thin film. This is a releasable base film for manufacturing thin metal films, which is provided with a release layer made of an amino copolymer resin and a copper phthalocyanine dye added to one surface of the heat-resistant synthetic resin film used.

The configuration of the present invention will be explained in more detail below.

First, each material used in the present invention will be described.

The heat-resistant synthetic resin film in the present invention is a well-known film such as a polyester film, a polyetherimide film, or a polyimide film, which are commonly used for depositing metal thin films by vacuum evaporation method, ion blating method, or sputtering method. It is readily available commercially. Although the thickness is not particularly limited, 12 to 75 μm is practically suitable.

Note that polyethylene film and polypropylene film are not used because they have poor heat resistance and cannot withstand the drying and curing temperature when forming the release layer.

The amino copolymer resin used in the present invention is a well-known one such as an aminoepoxy resin, an aminoalkyd resin, an aminoacrylic resin, or a urea melamine resin.More specifically, as an aminoepoxy resin, For example, a mixed resin of a butylated urea resin and an epoxy resin, an aminoalkyd resin such as a mixed resin of a butylated urea melamine cocondensation resin and a coconut oil-modified alkyd resin, an aminoacrylic resin such as a butylated resin, etc. Examples of the mixed resin of melamine resin and hydroxy methacrylic resin and urea melamine resin include butylated urea melamine cocondensation resin, and both are easily available from commercial products.

The copper phthalocyanine dye in the present invention refers to a copper phthalocyanine dye and a dye in which part of the copper in the molecular structure of the copper phthalocyanine dye is replaced with another metal. A specific example of the former is Neozapon Blue FLE (product name: BASF
A specific example of the latter is Neozapon Green 3GC (trade name: BASF, West Germany).

The metals in the present invention include Cυ, AI, Ag,
Targets single metals such as Au, Ni, and Ti, and alloy metals such as Ag-Pd, Fe-Ni, and stainless steel, which can be deposited by vacuum evaporation, ion blasting, or sputtering. It can be done.

The metal oxide in the present invention may be a metal oxide such as ITO or a metal oxide such as iron oxide, which can be deposited by any one of vacuum evaporation, ion blasting, and sputtering.

Next, the releasable base film for producing metal thin films according to the present invention will be described. This base film can be manufactured according to a conventional method except for using the copper phthalocyanine dye.

That is, a well-known organic solvent (for example,
Add the required amount of toluene, methyl ethyl ketone, isopropyl alcohol, etc.), the required amount of a well-known organic acid catalyst (for example, p-+-luenesulfonic acid, etc.) used as necessary, and the required amount of the copper phthalocyanine dye. The resulting paint is applied to a desired coating thickness using, for example, a roll coater, and dried and cured to form a release layer.

The amount of the copper phthalocyanine dye added is important, and it should be at least 0.01% by weight relative to the amount of the amino copolymer resin used, and if it is less than 0.01%, the peelability will be improved. is not recognized. It should preferably be at least 0.2%, but not more than 40%. Approximately 4
If it exceeds 0%, the adhesion between the heat-resistant synthetic resin film and the release layer will deteriorate. The coating thickness is not particularly limited, but
Dry film thickness of about 0.05 to 5.00 μm, preferably 0
．． The thickness is preferably 10 to 3.00 μm. Approximately 0゜05μm
If it is less than 5.00, the releasability between the surface of the mold release layer and the surface of the metal thin film layer will be poor, making it difficult to obtain a defect-free metal thin film;
If it exceeds μm, it takes too much time to dry and harden the coating film.

The temperature and time required for drying and curing the coating film mainly depend on the type and amount of the amino copolymer resin used, but are usually selected within the range of 150 to 200 DEG C.Cl2O to 50 seconds.

In addition, when forming the paint, if necessary, it is possible to color it by using other solvent-soluble dyes together with the copper phthalocyanine dye. Examples of this dye include Orazole Yellow 3R ( Trade name: cobalt complex dye: Ciba Geigy, Switzerland), Orazole Red B (trade name: nichrome complex dye: Ciba Geigy, Switzerland), and the like. When using these dyes in combination, the amount used should be kept to about half or less of the required amount of the copper phthalocyanine dye, and if it exceeds about half, the peelability between the release layer surface and the metal thin film layer surface will be poor. Become.

Furthermore, the other side of the heat-resistant synthetic resin film may be subjected to antistatic treatment according to a conventional method, if necessary.

Next, a method for manufacturing a metal thin film according to the present invention will be described.

In this manufacturing method, the desired metal thin film can be obtained in accordance with a conventional method, except for using the releasable base film for manufacturing a metal thin film according to the present invention.

That is, the metal or the metal oxide is vapor-deposited to a required thickness on the release layer surface of the releasable base film for manufacturing a metal thin film according to the present invention to form a metal thin film layer, and then the metal By peeling the thin film layer from the surface of the mold release layer, a metal thin film of the required thickness can be obtained.

The metal or metal oxide may be deposited by any of the well-known vacuum deposition methods, ion blating methods, and sputtering methods, and the deposition conditions may be any of the usual ones, as shown in the Examples below. good.

However, in the present invention, the thickness of the deposited film must be at least 50 Å, and if less than 50 people are involved, there is a risk that the resulting metal thin film will be defective when peeled off from the surface of the release layer. be.

The upper limit of the film thickness is not particularly limited.

In addition, in the case of a thickness exceeding about 5,000 mm, it is possible to obtain a metal thin film without defects and with no release layer residual odor attached even without using the present invention. .

[Effect]

According to the present invention configured as described above, an extremely thin metal thin film with a thickness of approximately 50 mm can be easily peeled off from the surface of the mold release layer without any defects and without any residual odor attached to the mold release layer. be able to. Unfortunately, the theoretical explanation of this phenomenon has not yet been elucidated, but based on the results of numerous experiments, the present inventors found that if the copper phthalocyanine dye is not present in the release layer, it is either impossible or impossible to remove it. (In this case, the beer ring checker
AD-1: Made by Kanzaki Paper ■: The peeling force measured by
On the other hand, if the copper phthalocyanine dye is present in the release layer, it can be easily peeled off without any defects (in this case, the peeling force measured using the same method as above is It has been confirmed that the surface resistance is approximately 5 to 20 gr), that no organic components are detected from the peeled surface, and that the surface resistance values of the evaporated surface and the peeled surface are equal, so we believe that this is due to the action of the copper phthalocyanine dye. There is.

[Example] Next, Examples and Comparative Examples will be given. In addition, "part" means a part by weight. Moreover, the peeling force is a value measured at a width of 24 m+n using the aforementioned peeling checker AD-1.

Example 1 10 parts of aminoacrylic resin (butylated melamine resin = 85 parts, hydroxy methacrylic resin: 15 parts), 30 parts of toluene, 30 parts of methyl ethyl ketone, 30 parts of isopropyl alcohol were added to one side of a 25 μm thick polyester film. A paint with a formulation consisting of 0.1 part of organic acid catalyst and 0.5 part of Neozapon Blue FLE (mentioned above) was applied using a roll coater at a dry film thickness of 0.5 μm, and The mixture was dried and cured with C for 30 seconds to form a release layer, thereby obtaining a release base film for producing metal thin films.

The surface of this mold release layer was colored pale blue.

Next, the degree of vacuum is 1. 5X10-'
At Torr, AI was deposited on the surface of the release layer of the base film to form an At thin film layer with a thickness of about 50 nm.

Next, 7 seconds after forming the thin film layer, the Ali film layer described in E was transferred to a glass plate coated with thermoplastic resin adhesive using a roll transfer machine, and the adhesive surface of the glass plate was The At thin film layer could be transferred without any defects and without peeling residue.

The peeling force of the AIM film layer at this time was 18 gr. Furthermore, no organic components were detected on the surface of the transferred Ali film.

Comparative Example 1 One side of a 25 μm thick polyester film was coated with a 0
．． A silicone layer with a thickness of 5 μm is formed, and the surface of this silicone layer is coated with a vacuum degree of 2x l O-'To using a vacuum evaporator.
A1 was deposited at rr to form an At thin film layer with a thickness of about 800 nm.

Next, an attempt was made to transfer the above All film layer in the same manner as in Example 1, but it was not possible to transfer the A1 thin film onto the adhesive surface of the glass plate.

Comparative Example 2 Example 1 except that Neozapon Blue FLE was not used
A base film with a release layer formed thereon was obtained in the same manner as above, and on the surface of the release layer of this base film, using a vacuum evaporator,
Vacuum degree 1. An At thin film layer having a thickness of approximately 700 nm was formed by depositing AI at 8×10-' Torr.

Next, when the above Aim film layer was transferred in the same manner as in Example 1, the At thin film was only partially transferred to the adhesive surface of the glass plate, and most of the At thin film layer was transferred to the release layer surface. remained in At this time, the peeling force of the At thin film could not be measured.

Example 2 10 parts of amino alkyd resin (butylated urea melamine cocondensation resin 280 parts, coconut oil modified alkyd resin: 20 parts) was applied to one side of a 50 μm thick polyester film.
30 parts of toluene, 30 parts of methyl isobutyl ketone, 30 parts of isopropyl alcohol, and Neozapon Green 3G
(Previously mentioned) A paint with a formulation consisting of 1 part was applied using a roll coater at a dry film thickness of 1.0 μm, and
A release layer was formed by drying and curing with C for 60 seconds to obtain a release base film for producing a metal thin film. The surface of this mold release layer was colored green.

Next, a sputtering device is used to reduce the vacuum degree to IX 10.
An ITO thin film layer having a thickness of approximately 700 mm was formed on the release layer surface of the base film at -'' Torr.

Next, in the same manner as in Example 1, the above ITO! When the film layer was transferred, the ITO thin film layer was transferred to the adhesive surface of the glass plate without any defects and without peeling residue. IT at this time
The peeling force of the Oi film layer was 13 gr. Also transcribed I
No organic components were detected on the surface of the Toff film.

Comparative Example 3 One surface of a 50 μm thick fluororesin film was vacuumed to a vacuum degree of I x 10-3T by sputtering.

An ITO thin film layer with a thickness of about 700 mm was formed using rr.

Next, in the same manner as in Example 1, when the above-mentioned ITO thin film layer was transferred, IT was partially applied to the adhesive surface of the glass plate.
o Only the thin film was transferred, but most of the ITO thin film layer remained on the film surface. The peeling force of the ITO thin film at this time was 300 gr.

Example 3 10 parts of aminoepoxy resin (0 parts of butylated urea resin, 30 parts of epoxy resin), 90 parts of the same solvent as in Example 1, and Neozapon Green 3G (previously) were applied to one side of a 75 μm thick polyester film. A paint with a formulation of 0.5 parts (1.5 parts) was applied using a roll coater to a dry film thickness of 0.5 μm, and dried and cured at 200°C for 45 seconds to form a release layer. A releasable base film for thin film production was obtained.

Next, using a vacuum evaporator, the vacuum degree is 1.2XIO-'T.
Cu was vapor-deposited on the release layer surface of the base film to form a Cu film layer with a thickness of about 3,500 mm.

Next, one month after forming the thin film layer, the above Cu film layer was transferred in the same manner as in Example 1, and the adhesive surface of the glass plate showed that the Cu thin film layer was free of defects and peelable. I was able to transcribe it without any problems. The peeling force of the Cum film layer at this time was 2gr.
Met. Further, no organic component was detected on the surface of the transferred Cu thin film.

Example 4 One side of a 38 μm thick polyester film was coated with a paint formulation consisting of 10 parts of butylated urea melamine cocondensation resin, 90 parts of the same solvent as in Example 1, and 0.1 part of Neozapon Blue FLE (described above). was applied using a roll coater to a dry film thickness of 0.5 μm, and dried and cured at 170° C. for 30 seconds to form a release layer to obtain a release base film for manufacturing thin metal films. .

Next, a sputtering device is used to reduce the vacuum degree to IX 10.
An ITO thin film layer having a thickness of about 1,000 wafers was formed on the release layer surface of the base film at -'' Torr.

The surface resistance value of this ITO thin film layer was measured and was 100.
It was Ω/d.

Next, 7 days after forming the thin film layer, the surface of the ITO thin film layer was peeled off using commercially available cellophane tape.
The TOm film layer was transferred to the adhesive surface of the cellophane tape without defects. When the surface resistance value of the transferred ITON film was measured, it was 100Ω/a! Met.

Comparative Example 4 Example 4 except that Neozapon Blue FLE was not used
A base film with a release layer formed thereon was obtained in the same manner as in Example 4, and an ITO thin film layer of about 1,000 thick was formed on the release layer surface of this base film in the same manner as in Example 4. An attempt was made to peel off using cellophane tape in the same manner as in Example 4, but no peeling occurred at all.

〔Effect of the invention〕

According to the present invention as described above, it is possible to easily obtain a metal thin film having a required thickness of about 50 Å or more without any defects, and the resulting metal thin film has release layer residue attached to it. The remarkable effect is that it does not.

Furthermore, since there is almost no change in releasability over time from the time of formation of the metal thin film layer to the time of peeling, it is possible to store the metal thin film in an unpeeled state until it is used.

Furthermore, the releasable base film for producing metal thin films according to the present invention can be produced continuously and efficiently using relatively inexpensive materials.

Claims (5)

[Claims] (1) Using a releasable base film in which a release layer made of an amino copolymer resin and a copper phthalocyanine dye is provided on one side of a heat-resistant synthetic resin film, metal or metal oxidation is applied to the surface of the release layer. A thin metal film or a thin metal oxide film is obtained by vapor-depositing a substance to form a thin metal film layer or a thin metal oxide film layer, and then peeling the thin metal film layer or metal oxide thin film layer from the surface of the release layer. Characteristic metal thin film manufacturing method. (2) Thickness of metal thin film or metal oxide thin film is 50 to 50
2. The method of manufacturing a metal thin film according to claim 1, wherein the thickness is 00 Å. (3) A releasable base film for manufacturing thin metal films, characterized in that a release layer made of an amino copolymer resin and a copper phthalocyanine dye is provided on one side of a heat-resistant synthetic resin film. (4) The releasable base film for producing metal thin films according to claim 3, wherein the heat-resistant synthetic resin film is any one of a polyester film, a polyetherimide film, and a polyimide film. (5) The releasable base film for producing metal thin films according to claim 3, wherein the amount of the copper phthalocyanine dye added is 0.01 to 40% by weight based on the amino copolymer resin.