JP2006007518A - Composite film of metal thin film and plastic film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite film of a metal thin film and a plastic film extremely excellent in the adhesiveness between the metal thin film and the plastic film. <P>SOLUTION: The composite film of the metal thin film and the polastic film contains the plastic film of which the surface is subjected to plasma treatment, the anchor coat layer provided on the plasma treated surface thereof and the metal thin film provided on the anchor coat layer. The anchor coat layer comprises aminosilane having primary and secondary amino groups. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is advantageously used for producing a flexible printed circuit board, an RFID (Radio Frequency ID) tag (wireless IC tag), and an IC card antenna pattern, particularly an RFID tag and an IC card antenna pattern for heat resistance. The present invention relates to a metal thin film / plastic film composite film that can be manufactured and a method for producing the same.

  In the electronics field, flexible printed wiring boards (FPC) have been used as wiring boards with metal thin film circuit patterns on plastic substrates, but recently compared to conventional magnetic tape and bar coating methods. Thus, an RFID tag (wireless IC tag), an IC card antenna pattern, and the like, which have a large storage capacity and can read information (data) from a certain distance, have come to be used. Such IC tags and IC cards are generally called non-contact type IC cards and IC tags, and have a large storage capacity and high reliability as described above. Further, these IC tags and IC cards are often required to have heat resistance, particularly from the viewpoint of manufacturing, like FPC. Polyimide is widely known as a heat-resistant polymer, and its properties include thermal, physical, chemical and thermal properties such as heat resistance, flame retardancy, mechanical strength, dimensional stability, chemical resistance, and electrical properties. Excellent electrical characteristics. For this reason, the above-mentioned application development is also expected.

  For example, a conventional flexible printed wiring board (FPC) has been manufactured by bonding a copper foil and an aluminum foil to a plastic film with an adhesive. Such a substrate has defects due to the adhesive, such as reduced adhesiveness under high temperature and high humidity, reduced flexibility, repeated electrical properties due to impurity ion contamination, and reduced chemical resistance. . In particular, when a metal thin film such as a copper foil having a very thin thickness is bonded using an adhesive, the metal thin film is likely to become wrinkles. Therefore, the bonding is usually performed only to a thickness of about 18 microns. Therefore, in FPC, since the thickness of the thin metal layer is increased, the cross section of the film after etching tends to be trapezoidal, and it is difficult to manufacture a fine circuit pattern.

  Such a problem can be similarly seen when a polyimide film is used as the plastic film in order to improve the heat resistance of the wiring board. A three-layer (polyimide / adhesive / metal thin film) FPC using such a polyimide film has problems in terms of adhesion, heat resistance, contamination, and reliability as compared to other plastic materials. For example, there is a problem that the heat resistance of the adhesive used is lower than that of the polyimide film; the mounting technology using FPC or the like is also the result of the high density mounting, and as a result, copper in the adhesive that could not have occurred in the past If an adhesive is used in order to further increase the number of FPC layers, the process becomes complicated and electrical bonding between layers occurs, resulting in problems of reliability of through-hole plating.

  The flexible printed wiring board (FPC) needs to have a narrow conductor width and a small thickness in consideration of the trend of electronic technology that will continue to become lighter and thinner. However, copper, which is mainly used as a material for the metal thin film, also has an electrical resistance. If the amount of heat generated thereby is not dissipated, the temperature rises indefinitely and destroys the element or insulation. In the future, circuits are expected to become finer and rise to very high temperatures, and heat resistance characteristics are increasingly required.

  Patent Document 1 proposes a method for improving the adhesive force between a polyimide film and a metal thin film without providing an adhesive layer between the polyimide film and the metal thin film. That is, this method includes a step of plasma-treating a surface of a polyimide film, a step of coupling the plasma-treated polyimide film with an imidazole silane solution of a silane coupling agent containing an imidazole group, and the coupling-treated polyimide film It is performed from the process of forming a metal thin film by sputtering or vapor-depositing a metal on the surface.

JP-A-11-29852

  According to the method described in Patent Document 1, it is possible to reduce the thickness and size of the wiring board, and not only the FPC but also the RFID tag (wireless IC tag) for heat-resistant or non-heat-resistant applications having a large storage capacity and the antenna pattern of the IC card. It is also useful for production. Furthermore, it is useful for the production of TAB (tape automated bonding), conductive composite films such as electrode films for large panels such as liquid crystal displays and high vision, and films for heating elements.

  However, the FPC of the polyimide film / coupling layer / metal thin film obtained by the method described in Patent Document 1 may not yet have sufficient adhesion of the metal thin film, and the obtained FPC can withstand practical use. It became clear that it was not limited.

  According to the study by the present inventors, in particular, the heat-resistant polyimide film has extremely low adhesion to copper, and even if the surface treatment shown in Patent Document 1 is performed, sufficient adhesion may not be obtained. It became clear.

  Therefore, the present invention has a fine printed circuit board (FPC), a RFID tag (wireless IC tag), a fine electronic circuit suitable for manufacturing an IC card antenna pattern, and the like, and a metal having excellent adhesion. The object is to provide a composite film of a thin film and a plastic film.

  In addition, the present invention includes a metal thin film and a plastic film that have fine electronic circuits suitable for the production of heat-resistant RFID tags (wireless IC tags) and IC card antenna patterns, etc., and are excellent in heat resistance and adhesiveness. It is an object of the present invention to provide a composite film.

  Furthermore, an object of the present invention is to provide a method for producing a composite film of the metal thin film and the plastic film.

The object is a composite film of a plastic film and a metal thin film comprising a plastic film having a plasma-treated surface, an anchor coat layer provided on the plasma-treated surface, and a metal thin film provided on the anchor coat layer. ,
The anchor coat layer can be achieved by a composite film characterized by comprising an aminosilane having a primary or secondary amino group.

In the composite film, the anchor coat layer is generally a layer having 0.01 to 0.09 g per 1 m ^{2 of} an amount (coating amount) of an aminosilane having a primary or secondary amino group. (The thickness of the anchor coat layer corresponds to 0.01 to 0.08 μm). Thereby, the high adhesiveness of a thin metal layer can be obtained. The aminosilane having the primary or secondary amino group is preferably an aminoalkoxysilane, particularly N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl). -3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine and at least one selected from N-phenyl-3-aminopropyltrimethoxysilane. Thereby, the high adhesiveness of a thin metal layer can be obtained.

  The anchor coat layer may be composed of an aminosilane having a primary or secondary amino group and an organic carboxylic acid having a carbon-carbon double bond (preferably a (meth) acrylic acid monomer). It is preferable for obtaining high adhesiveness. The anchor coat layer is generally a cured product of an aminosilane having a primary or secondary amino group. The metal thin film is usually a vapor deposited metal film, and the present invention is particularly effective. When the metal of the metal thin film is copper, the effect of improving the adhesiveness of the present invention is easily obtained. The thickness of the metal thin film is generally 0.1 to 10 μm. The plasma treatment is preferably a plasma treatment performed in the presence of at least one of argon, helium, nitrogen, and oxygen. Similarly, it is useful for improving the adhesion of metal thin films. The plastic film is preferably a heat resistant plastic film, particularly a polyimide film. Such a heat-resistant film exhibits particularly excellent adhesion.

  In the present invention, the surface of the polyimide film is plasma-treated, and a solution containing aminosilane having primary or secondary amino groups is applied to the plasma-treated surface, followed by drying and curing to form an anchor coat layer. In addition, there is also a method for producing a composite film of a metal thin film and a polyimide film, comprising forming a metal thin film by depositing a metal on the anchor coat layer.

In the production method, the aminosilane-containing solution is generally a 0.02 to 0.30% by mass solution of aminosilane, particularly a 0.04 to 0.20% by mass solution. As a result, an appropriate amount of an aminosilane layer that contributes to improved adhesion can be formed. It is preferable that the coating amount after drying of the solution containing the aminosilane is 0.01 to 0.09 g per 1 m ² .

  The aminosilane having the primary or secondary amino group is an aminoalkoxysilane, particularly N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- It is preferably at least one selected from (dimethylbutylidene) propylamine and N-phenyl-3-aminopropyltrimethoxysilane.

  Furthermore, the solution containing the aminosilane further contains 0.1 to 1.0% by mass of an organic carboxylic acid, generally an organic carboxylic acid having a carbon-carbon double bond (preferably a (meth) acrylic acid monomer). preferable. This also improves the adhesion of the thin metal layer.

  When the metal of the metal thin film is copper, the effect of improving the adhesiveness of the present invention is easily obtained. The thickness of the metal thin film is generally 0.1 to 10 μm. The plasma treatment is preferably a plasma treatment performed in the presence of at least one of argon, helium, nitrogen, and oxygen. Similarly, it is useful for improving the adhesion of metal thin films.

    The composite film of the metal thin film and the plastic film of the present invention has extremely excellent adhesion between the metal thin film and the plastic. Among plastic films, it exhibits excellent adhesion to heat-resistant plastic films, particularly polyimide films. For this reason, when this composite film is used to produce antenna patterns for flexible printed wiring boards, RFID tags (wireless IC tags) and IC cards, or those antenna patterns for heat-resistant applications, There is no occurrence of defects such as peeling, and the obtained product has excellent adhesion of the metal thin layer, and can be sufficiently put into practical use. Moreover, the manufacturing method of this invention can manufacture this composite film easily.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of an embodiment of a metal thin film / plastic film composite film of the present invention. FIG. 1 shows a composite of a plastic thin film and a plastic film comprising a plastic film 1, an anchor coat layer 2 provided on the plasma-treated surface, and a metal thin film 3 formed on the surface of the anchor coat layer 2. The film is shown. The plastic film 1 is preferably a heat resistant plastic film, particularly a polyimide film. The anchor coat layer 2 is an extremely thin film and is made of a specific aminosilane (silane coupling agent) having a primary or secondary amino group. Generally, these aminosilanes are bonded and cured by reacting between the aminosilanes and between the plasma-treated surfaces of aminosilane and polyimide. A metal thin film 3 is formed on the surface of the plastic film 1 with the anchor coat layer 2 interposed therebetween. For this reason, the metal thin film 3 and the plastic film 1 are firmly bonded. The metal thin film 3 is generally formed by vapor deposition.

  The metal thin film / plastic film composite film of the present invention can be produced, for example, according to the following steps (1) to (3).

(1) a step of plasma treating the surface of the plastic film;
(2) Applying a solution containing aminosilane having a primary or secondary amino group to the plasma treated surface, drying and curing to form an anchor coat layer; and (3) on the anchor coat layer. A process of forming a metal thin film by depositing metal.

  A well-known material can be used as a plastic film used at the said process (1). For example, polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis (2-chlorophenoxyethane-4,4′-dicarboxylate), polyphenylene sulfide, polyether sulfone, polyether ketone And films made of aromatic polyamide, polyarylate, polyimide, polyamideimide, polyetherimide and the like. In the present invention, a heat resistant film is preferable, and a polyimide film is particularly preferable. Examples of polyimides include wholly aromatic polyimides and bismaleimide polyimides, and wholly aromatic polyimides are preferred. In particular, polyimide obtained from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether (eg, trade name Kapton manufactured by Toray DuPont) is preferable. The polyimide film is preferably excellent in properties such as strength and elongation. For example, the strength is preferably 200 MPa or more (JIS-C-2318) and the elongation is 60% or more (JIS-C-2318).

  The plasma treatment in the step (1) can be performed using, for example, a parallel plate electrode type (capacitance (C) coupling type) radio frequency (RF) plasma apparatus. For example, in a bell jar that is decompressed and maintained at a constant pressure during plasma processing, the above plastic film is placed on an electrode plate, and a plasma atmosphere is created by applying a voltage between the electrodes by a high frequency power source. The film is plasma treated by supplying. In addition to the above-described capacitive (C) coupled RF plasma device, a DC DC plasma device, a microwave plasma device, an inductive (L) coupled RF plasma device, or the like can be used.

  Examples of the gas that can be used for the plasma treatment include argon, helium, nitrogen, and oxygen. Each is used alone or in combination of two or more. Argon, helium, nitrogen and oxygen are preferably used alone or in combination of argon and nitrogen, argon and oxygen, nitrogen and oxygen.

The output of the high frequency (13.56 MHz) power source in the plasma treatment is preferably in the range of 10 W to 200 W, particularly in the range of 50 to 150 W. If the output exceeds 200 W, the plasma treatment is too strong, and even a heat-resistant film such as a polyimide film is likely to deteriorate. On the other hand, if it is less than 10 W, the output is too weak and the plasma treatment effect is small. The pressure in the plasma treatment is in the range of atmospheric pressure ^{to 10 -2} torr is ^common, preferably ¹⁰ -1 ^{~10 -2} torr. When the pressure is outside the above range, plasma is hardly generated and the treatment effect is small. The irradiation time of the plasma treatment is in the range of 10 seconds to 20 minutes, preferably in the range of 20 seconds to 10 minutes. If it is less than 10 seconds, the treatment effect is small. On the other hand, if it is longer than 20 minutes, even a heat resistant film such as a polyimide film is likely to deteriorate.

  The plasma processing system used in the present invention is not limited to the batch processing apparatus described above, and a plasma continuous processing apparatus in which film unwinding and winding are installed inside a vacuum chamber, or a film unwinding and winding mechanism are provided. An external plasma processing system such as an air-to-air system can be used.

  When the above plasma treatment is performed on, for example, a polyimide film, cleavage of the imide ring of the polyimide film occurs, and when the site is exposed to air, a carboxyl group and a hydroxyl group are generated by reacting with moisture in the air. It is considered that the efficiency of the coupling treatment with the specific aminosilane agent of the present invention in this step is increased.

  The application, drying, and curing of the solution containing aminosilane having a primary or secondary amino group on the plasma-treated surface in the step (2) is performed as follows, for example. First, the aminosilane of the present invention is dissolved in an organic solvent such as methanol to prepare a coating solution. The aminosilane-containing solution is generally a 0.025 to 0.25% by mass aminosilane solution, particularly preferably 0.05 to 0.10% by mass. As a result, a thin and uniform layer can be obtained, and a layer of an appropriate amount of aminosilane that contributes to improvement in adhesion can be easily obtained. As the organic solvent, alcohols such as methanol and ethanol are preferable, and esters, ketones, ethers, hydrocarbons, and water can be used as necessary.

After apply | coating the obtained coating solution on the surface of a plastic film, the obtained coating layer is heat-dried and hardened. This makes it possible to form an aminosilane layer having an appropriate amount for improving the adhesion. The coating amount after drying of the coating solution (that is, the formed undercoat layer is the amount of aminosilane having a primary or secondary amino group) is 0.01 to 0.09 g per 1 m ² , especially 0.8. It is preferable that it is 03-0.06g.

  As the coating method of the coating solution, any known coating method can be used. For example, gravure roll coating, roll coating, spray coating, dipping method and the like can be used. After the coating, drying and curing are performed at 50 to 150 ° C., preferably 90 to 120 ° C., for 1 to 30 minutes, preferably 2 to 10 minutes. After curing, if necessary, unreacted aminosilane may be washed with methanol using an ultrasonic cleaner or the like.

  The aminosilane having the primary or secondary amino group is generally an aminoalkoxysilane, and preferred examples thereof include N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (amino Ethyl) -3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- Mention may be made of (1,3-dimethylbutylidene) propylamine and N-phenyl-3-aminopropyltrimethoxysilane. In particular, N-phenyl-3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane are preferable. These may be used alone or in combination.

  The reason why the adhesion between the metal thin film of the present invention and the polyimide film surface is greatly improved is considered as follows. On the surface of the polyimide film plasma-treated as described above, carboxyl groups, hydroxyl groups, etc. are formed, and the primary or secondary amino groups of the aminosilane of the present invention react with this during curing, and this As a result, the surface of the polyimide film has a high affinity with the metal, and the adhesion of the thin metal layer is improved. In this case, formation of a carboxyl group on the surface of the polyimide film is considered particularly effective. Alternatively, the alkoxyl group of the silane coupling agent may be hydrolyzed to form silanol to form a hydrogen bond or a chemical reaction with the metal thin film. A similar reaction is considered to occur in plastic films other than polyimide films.

  Furthermore, the coating solution containing the aminosilane further contains an organic carboxylic acid, generally an organic carboxylic acid having a carbon-carbon double bond, preferably a (meth) acrylic acid monomer, particularly acrylic acid or methacrylic acid. It is preferable to contain 0.0 mass%. This also improves the adhesion of the thin metal layer.

Next, in the step (3), a metal thin film is formed on the surface of the plastic film that has been subjected to the plasma treatment and the coating process of the anchor coat layer in the steps (1) and (2). The metal thin film is formed by depositing a metal. As the evaporation method, vacuum evaporation, sputtering, electron beam evaporation, ion plating, or the like can be used, and various methods can be used. The electron beam evaporation method is particularly preferable. As conditions for vapor deposition, the pressure is preferably 10 ⁻⁴ to 10 ⁻⁶ torr. The deposition rate is preferably in the range of 2 to 50 liters / second, preferably 10 to 30 liters / second. When the rate is smaller than the above range, it takes too much time for vapor deposition. When the rate is larger than the above range, the metal thin film is not dense.

  Examples of the metal forming the metal thin film include copper, chromium, nickel, palladium and the like. Copper is preferred. When the metal of the metal thin film is copper, the effect of improving the adhesiveness of the present invention is easily obtained. The thickness of the metal thin film is generally 0.1 to 10 μm, preferably 0.1 to 5 μm. Thereafter, when the thickness of the metal thin film is further required, it may be thickened by electroless plating or electrolytic plating.

In the case of the general thickness, the electroless plating is performed under the following conditions, for example:
Copper compound: Copper oxide CuO (2.0 g / L as Cu)
Complexed product: EDTA (ethylenediaminetetraacetate; 74 g / L)
Reducing agent: Paraformaldehyde (5 g / L as HCOH)
pH adjuster: KOH (adjusted to pH = 12.5)
Stabilizer: 2,2′-bipyridine (10 mg / L)
Additive: PEG-1000 (polyethylene glycol; 100 mg / L)
Plating bath temperature: 60 ° C
Plating thickness: 3-50 μm
Performed in
For general thinning, for example, the following conditions:
Copper compounds: copper sulfate CuSO ₄ · _5H 2 O (Cu as 2.5 g / L)
Complex of: Rochelle salt _{(KNaC 4 H 4 O 6 ·} 4H 2 O; 16g / L)
Reducing agent: formalin (37% solution; 10 g / L as HCHO)
pH adjuster: NaOH (adjusted to pH = 13.0)
Stabilizer: Sodium cyanide (NaCN; 10 mg / L)
Additive: Thiomalic acid (HSCHCOOHCH ₂ COOH; 1 mg / L)
Plating bath temperature: 25 ° C
Plating thickness: 0.5-3 μm
It is done at.

  When the thickness of the metal thin film is further increased by electroless plating, the deposition rate of copper is slow under the electroless plating thinning condition, and therefore it is generally performed under the thickening condition.

In the case of the electroplating, for example, it is performed as follows:
(Composition of plating bath)
Copper sulfate: 200-250 g / L
Metallic copper: 50-62 g / L
Sulfuric acid: 35-75 g / L
Sulfuric acid / copper copper: about 1/1
Chlorine: 20-40mg / L
Additive: Appropriate amount of brightener, etc. (plating conditions)
Bath temperature: 20-50 ° C
Cathode current density: 1 to 10 Å / dm ²
Anode current density: 0.5-5 Å / dm ²

  It carries out, stirring a plating bath on the said conditions.

  The composite film of the metal thin film and plastic film of the present invention obtained as described above is extremely excellent in adhesion between the metal thin film and the plastic film (particularly polyimide film). For this reason, using this composite film, When a flexible printed circuit board, a heat resistant RFID tag (wireless IC tag) and an IC card antenna pattern, or a heat resistant antenna pattern are produced, there is no occurrence of defects such as peeling of a thin metal layer during the production. In addition, the product obtained has excellent adhesiveness of the thin metal layer, and can sufficiently withstand practical use.

  The following examples further illustrate the present invention.

[Example 1]
<Production of composite film having circuit pattern>
(1) A plasma treatment was performed on a polyimide film (Kapton 200V: manufactured by Toray DuPont) with a thickness of 50 μm under the following conditions.

[Plasma treatment conditions]
Plasma equipment: Parallel plate electrode type RF plasma equipment
(Product name: Low pressure plasma device SKN-05P; manufactured by Nippon Radio Frequency Co., Ltd.)
Frequency: 13.56 MHz; Output: 100 W;
Pressure: 1 torr; Gas: Ar; Irradiation time: 5 minutes

(2) A coating solution for forming an anchor coat layer having the following composition is applied to the plasma-treated surface of the obtained polyimide film using a gravure coater, and heated at 110 ° C. for 5 minutes for drying and curing. An anchor coat layer having a thickness of 0.05 g / m ² was formed.

[Composition of coating solution for anchor coat layer formation]
N-phenyl-3-aminopropyltrimethoxysilane 0.100 parts by mass (KBM-573; manufactured by Shin-Etsu Chemical Co., Ltd.)
99.900 parts by mass of methanol

(3) On the anchor coat layer of the polyimide film provided with the obtained anchor coat layer, a Cu thin metal layer (thickness: 2 μm) was formed under the following conditions.

[Cu deposition conditions]
Electron beam evaporation system: Product name: EGL-35M; manufactured by ULVAC Corporation)
Output: 8 KW; Pressure: 10 ⁻⁵ torr; Deposition rate: 25 Å / sec A metal thin film / polyimide film composite film was obtained as described above.

[Examples 2 to 24 and Comparative Examples 1 to 17]
In Example 1, except that the plasma treatment conditions in (1) and the coating solution for forming an anchor coat layer in (2) were changed as shown in Table 1 or Table 2, the metal thin film / polyimide film was similarly used. A composite film was obtained. The amount of methanol in the coating solution was added so that the total amount of the solution was 100 parts by mass.

<Evaluation of Adhesiveness of Composite Film of Obtained Metal Thin Film / Polyimide Film>
First, the surface of an aluminum plate (thickness: 0.5 mm) is degreased with acetone, and two thermoplastic resin films (thickness: 50 μm; Himiran 1652; manufactured by Mitsui DuPont Polychemical Co., Ltd.) are stacked on top of this. The composite film obtained above was placed on the surface of the thermoplastic resin film so that the metal thin film faces the thermoplastic resin film.

The laminated body was press-bonded for 5 minutes under the conditions of 200 ° C. and 100 Kgf / cm ² with a hot press to prepare an adhesive evaluation sample. A mini test press 10 manufactured by Toyo Seiki Co., Ltd. was used as a heat press apparatus.

  The sample was subjected to a tensile test under the following conditions, and the force when peeled between the metal thin film and the polyimide film was measured.

[Tensile test measurement conditions]
Tensile test device: Shimadzu Autograph AGS-D series Air pressure: 4Kgf / cm ² , Tensile speed: 100mm / cm
The said test was done based on the peel strength test method (180 degree peel test method) of the adhesive agent of JIS-K-6854.
The test results obtained are shown in Tables 1 and 2.

Abbreviations in Tables 1 and 2 are as follows:
VTMS: Vinyltrimethoxysilane
GPTES: 3-glycidoxypropyltriethoxysilane
PAPTMS: N-phenyl-3-aminopropyltrimethoxysilane
APTMS: 3-aminopropyltrimethoxysilane
IS-3000: trialkoxysilyl type imidazolesilane containing secondary hydroxyl group,
Made by Nikko Materials Co., Ltd.
IS-4000: Secondary hydroxyl group-containing trialkoxysilyl type imidazole silane,
Low pressure: 1 torr made by Nikko Materials Co., Ltd.
Atmosphere: Atmospheric pressure Other conditions are the same as in Example 1. However, in Comparative Examples 18 to 21, heating for drying and curing the coating layer of the coating solution for forming the anchor coat layer was performed at 110 ° C. for 90 minutes.

  As shown in Tables 1 and 2, after the surface of the polyimide film of the present invention was plasma-treated, only when the anchor coat layer of the specific aminosilane of the present invention was formed, excellent adhesion of the Cu thin metal layer was gotten. As shown in the comparative example, when only the plasma treatment was used or when a silane coupling agent other than the present invention was used, sufficient adhesiveness could not be obtained.

It is sectional drawing which shows an example of embodiment of the composite film of the metal thin film / polyimide film of this invention.

Explanation of symbols

1 Plastic film 2 Anchor coat layer 3 Metal thin film

Claims (20)

A composite film of a metal thin film and a plastic film, comprising a plastic film whose surface is plasma treated, an anchor coat layer provided on the plasma treated surface, and a metal thin film provided on the anchor coat layer,
The composite film, wherein the anchor coat layer is composed of an aminosilane having a primary or secondary amino group.   The composite film according to claim 1, wherein the aminosilane having a primary or secondary amino group is an aminoalkoxysilane.   The aminosilane having the primary or secondary amino group is N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and N The composite film according to claim 1 or 2, which is at least one selected from -phenyl-3-aminopropyltrimethoxysilane.   The composite film according to any one of claims 1 to 3, wherein the anchor coat layer comprises an aminosilane having a primary or secondary amino group and an organic carboxylic acid having a carbon-carbon double bond.   The composite film according to any one of claims 1 to 4, wherein the anchor coat layer comprises a cured product of an aminosilane having a primary or secondary amino group. The composite film according to any one of claims 1 to 5, wherein the anchor coat layer has a thickness corresponding to a coating amount of 0.01 to 0.09 g per 1 m ² .   The composite film according to claim 1, wherein the metal thin film is a vapor-deposited metal film.   The composite film according to claim 1, wherein the metal of the metal thin film is copper.   The film thickness of the said metal thin film is 0.1-10 micrometers, The composite film in any one of Claims 1-8.   The composite film according to claim 1, wherein the plasma treatment is a plasma treatment performed in the presence of at least one of argon, helium, nitrogen, and oxygen.   The composite film according to claim 1, wherein the plastic film is a polyimide film.   The surface of the plastic film is plasma treated, a solution containing aminosilane having primary or secondary amino groups is applied to the plasma treated surface, dried and cured to form an anchor coat layer, and the anchor coat A method for producing a composite film of a metal thin film and a plastic film, wherein a metal thin film is formed by vapor-depositing a metal on the layer.   The manufacturing method according to claim 12, wherein the solution containing aminosilane is a 0.020 to 0.30 mass% solution of aminosilane. The manufacturing method according to claim 13, wherein the coating amount after drying of the solution containing aminosilane is a thickness corresponding to a coating amount of 0.01 to 0.09 g per m ² .   The method according to any one of claims 12 to 14, wherein the aminosilane having a primary or secondary amino group is an aminoalkoxysilane.   The aminosilane having the primary or secondary amino group is N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and N The production method according to claim 12, which is at least one selected from phenyl-3-aminopropyltrimethoxysilane.   The production method according to any one of claims 12 to 16, wherein the solution containing the aminosilane further contains 0.1 to 1.0% by mass of an organic carboxylic acid having a carbon-carbon double bond.   The manufacturing method according to claim 12, wherein the metal of the metal thin film is copper.   The manufacturing method according to any one of claims 12 to 18, wherein the plasma treatment is performed in the presence of at least one of argon, helium, nitrogen, and oxygen.   The composite film according to claim 12, wherein the plastic film is a polyimide film.

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