JP2014019153A - Laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate film which can be used favorably on occasions for forming electrode metals used for electronic appliances, etc., specifically a laminate film for circuits resistant to occurrences of defects such as line dropouts or line depletions of pattern shapes when metal layers serving as electrodes are processed into pattern shapes at wet process steps such as etching, etc.SOLUTION: In a laminate film comprising a resin film (A) 3, a resin layer (B) 1, and a metal layer (C) 2 in proper order, the 90-degree peeling strength Fof the metal layer (C) at 23°C and 50%RH is 0.5 N/cm or above, and, when the 90-degree peeling strength of the metal layer (C) within water is defined as F, the ratio F/Fis 0.8 or above.

Description

  The present invention relates to a laminated film suitable for a touch panel, an electromagnetic wave shield, a receiving antenna, an electric heater, and the like.

  As a conductive film used for a touch panel or an electromagnetic wave shield, a film in which a metal layer having an arbitrary pattern shape is provided on a resin film such as a polyester film is known. In particular, circuit materials using a transparent film have been proposed for various applications such as automobiles and displays because of their light weight and good visibility.

  As a method for producing this conductive film, a metal foil such as a copper foil is laminated on a transparent film via an adhesive layer, a resist film is pasted, and after exposure through a photomask having a desired pattern shape, development is performed. A method of providing a patterned metal layer on a transparent film using a photolithographic method for etching, resist peeling (see Patent Document 1) is known.

  Among them, in the method of laminating a transparent film and a metal foil (copper foil), a metal foil having a thickness of about 10 μm or more is usually used in order to achieve uniform bonding, but a metal foil having a thickness of 10 μm or more. When a pattern shape having a comparatively small line width (for example, less than 10 μm) is created by etching, a metal foil (copper foil) having a thickness of 5 μm or less is expensive, or a transparent film and a metal foil are laminated. The problem is that the fine irregularities on the surface of the metal foil are transferred to the opening of the adhesive layer (the part where the metal foil has been removed by etching) and the transparency deteriorates. In the case of an inexpensive metal foil, the thickness is 10 μm. There is a problem that it is difficult to reduce the line width due to the increase in thickness.

  In response to the above problems, a metal layer is directly formed on a polyester film such as polyethylene terephthalate by a vapor deposition method, and a thin line pattern is formed on the metal layer using a printing method, a photolithography method, an etching method, or the like. A method of forming a metal layer having a pattern shape by processing has been proposed. In this method, high conductivity can be obtained even with a metal layer having a relatively small thickness (for example, 4 μm or less). Therefore, by reducing the thickness of the metal layer, the workability of the fine line pattern is improved and the line width is relatively large. It is possible to easily form a high-definition pattern shape with a small (for example, less than 10 μm).

  For example, Patent Documents 2 and 3 describe a method for forming a patterned metal layer using the metal layer formed by the above vapor deposition method.

  On the other hand, in order to improve adhesion between a substrate such as a transparent film and a metal layer, it is known that a laminated film such as a primer layer is provided on the substrate in advance (for example, Patent Documents 4 to 7).

  Patent Document 4 discloses a method for producing an electromagnetic wave shielding film in which an undercoat layer made of a urethane resin is applied to a molded article such as ABS resin or polycarbonate, and a metal layer is vacuum-deposited thereon. Patent Document 5 It is disclosed that a primer layer made of an epoxy resin, a polyester resin, a phenol epoxy resin, an acrylic resin, a urethane resin, or the like is provided on a transparent film, and a conductive treatment layer is formed thereon by vacuum deposition. An optical polyester film provided with a coating layer composed of an acrylic resin and a crosslinking agent on a film is applied to a conductive film for a plasma display. Patent Document 7 discloses a urethane resin on a transparent substrate made of a polyamide resin or the like. And a primer layer containing epoxy resin, and an electromagnetic shielding film is formed on it. It discloses an electromagnetic wave shielding molded product.

Japanese Patent No. 3388682 JP 2004-95829 A JP 2005-268688 A JP 2003-112388 A Japanese Patent Application Laid-Open No. 2004-253587 JP 2005-89622 A JP 2007-173736 A

  However, the pattern-shaped metal layer produced by the methods described in Patent Documents 2 and 3 has a problem of peeling and dropping of the pattern-shaped metal layer due to adhesion with a polyester film used as a transparent film. It was. In particular, in the wet process (for example, resist development, etching, resist stripping, blackening treatment, etc.) in the manufacturing process of the patterned metal layer, the above-described problem of stripping of the metal layer is likely to occur. In addition, the adhesion between the polyester film and the pattern-shaped metal layer in the wet process described above is reduced, so that the pattern-shaped metal layer is easily peeled off and dropped off in subsequent handling and post-processing of the conductive film. There is a problem that dry adhesion is deteriorated.

  In addition, in the methods described in Patent Documents 4 to 7, the adhesion of the pattern-shaped metal layer targeted by the present invention cannot improve the dropout or chipping of the pattern during the etching process or washing with water or during the transport process. There's a problem.

  Therefore, in view of the above-described conventional technology, the object of the present invention is to prevent defects such as line dropping in an etching process, etc., and to obtain a high-definition pattern shape at a low cost, and a transparent film or the like. An object of the present invention is to provide a laminated film having improved adhesion between a resin film as a base material and a patterned metal layer.

The above object of the present invention has been basically achieved by the following invention.
1) A laminated film having a resin film (A), a resin layer (B), and a metal layer (C) in this order,
Metal layer (C), 23 ° C., and 90 ° peel strength _{F 1} under 50% RH is 0.5 N / cm or more, the metal layer (C), a 90-degree peel strength in water and _{F 2} A laminated film, wherein the ratio F ₂ / F ₁ is 0.8 or more.
2) Resin layer (B) has acrylic resin (B) which has a urethane bond as a main component, The laminated film as described in 1) characterized by the above-mentioned.
3) The acrylic resin (B) having a urethane bond is an acrylic resin obtained by reacting an acrylic resin (b) having a hydroxyl group with an isocyanate compound,
The laminated film according to 2), wherein the acrylic resin (b) having a hydroxyl group has a glass transition temperature of 30 ° C. or higher and 80 ° C. or lower.
4) The laminated film according to any one of 1) to 3), wherein the resin layer (B) has a thickness of 0.05 to 5 μm.
5) Thickness of said metal layer (C) is 0.05-10 micrometers, The laminated film in any one of 1) -4) characterized by the above-mentioned.
6) The laminated film according to any one of 1) to 5), wherein the metal layer (C) has a pattern shape.

  According to the present invention, it is possible to prevent defects such as line dropout and chipping in an etching process, etc., obtain a high-definition pattern shape at low cost, and a resin that is a pattern-shaped metal layer and a substrate A laminated film having improved adhesion to the film can be provided. In addition, by using the laminated film of the present invention, it becomes possible to apply and form a bonding layer such as an adhesive on the metal layer of the laminated film, whereby a circuit film having good light transmittance at low cost. Can be provided.

The schematic diagram of the laminated | multilayer film of this invention.

The laminated film of the present invention is a laminated film having a resin film (A), a resin layer (B), and a metal layer (C) in this order, and the metal layer (C) is at 23 ° C. and 50% RH. The 90 ° peel strength F ₁ is 0.5 N / cm or more, and the ratio F ₂ / F ₁ is 0.8 or more when the peel strength in water of the metal layer (C) is F _2. It is characterized by that. Hereinafter, each requirement will be described.

  The resin film (A) is not particularly limited as long as it is generally referred to as a polymer resin film. The resin constituting the resin film (A) is preferably a polyester sheet having excellent optical properties such as transparency, polycarbonate (PC), polycycloolefin, and bisphenol A as a main monomer. Further, the resin film (A) may be a film obtained by bonding a plurality of resin films. Among these, polyester is preferable as the resin constituting the resin film (A) from the viewpoints of excellent flexibility, low cost, high transparency, and excellent heat resistance and chemical resistance.

  Here, the term “polyester” is a general term for polymers having an ester bond as the main bond chain of the main chain. Examples of such polyester include ethylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, ethylene-α, β-bis (2-chlorophenoxy) ethane-4,4-dicarboxylate, and the like. Among these, polyesters containing ethylene terephthalate are particularly preferable in view of quality and economy.

  The resin film (A) has various known additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers. Further, an antistatic agent, a nucleating agent and the like can be contained to such an extent that the effects of the present invention are not impaired.

Moreover, it is preferable that the thickness of a resin film (A) is 25 micrometers-250 micrometers, More preferably, they are 100 micrometers-200 micrometers.

The laminated film of the present invention is a laminated film having a resin film (A), a resin layer (B), and a metal layer (C) in this order. As long as the laminated film of the present invention has the resin film (A), the resin layer (B), and the metal layer (C) in this order, there is no particular problem even if other layers exist. The laminated film of the present invention preferably has an embodiment in which a resin film (A), a resin layer (B), a base layer described later, and a metal layer (C) are directly laminated in this order.

The method for forming the metal layer (C) is not particularly limited, but for example, it can be formed by a vapor deposition method. Examples of the vapor deposition method include sputtering, ion plating, electron beam vapor deposition, vacuum vapor deposition by induction heating, chemical vapor deposition, and the like. These one method or a combination of two or more methods can be used. When forming the metal layer (C), any method selected from the group consisting of sputtering, ion plating, and vacuum deposition is preferred, and sputtering and / or vacuum deposition are particularly preferred.

Since the metal layer (C) according to the present invention is preferably a layer having high conductivity, it is important that the thickness of the metal layer (C) is 0.05 μm or more. As a metal constituting the metal layer (C), an alloy or a multi-layered one or a combination of two or more of metals such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium and titanium is used. Can be used. Among these, copper is preferably used as the metal constituting the metal layer (C) from the viewpoint of easy processing into a pattern shape and low cost.

When copper is used as the metal constituting the metal layer (C), that is, when the metal layer (C) is a copper layer, the metal layer (C) is formed after the base layer is formed on the resin layer (B). Is preferred. Here, the underlayer is a layer composed of at least one metal selected from the group consisting of nickel, chromium, and nichrome, and means a layer having a thickness of 5 to 100 nm. The resin layer (B) and the metal layer (C) (copper layer) are laminated through such an underlayer (that is, the resin layer (B) / underlayer / metal layer (C) (copper layer)) Directly laminating in this order is preferable because the adhesion between the resin layer (B) and the metal layer (C) (copper layer) is further improved.

In the case of a conventional laminate of a metal layer and a resin film, there is a problem that the adhesion between a metal layer formed by a vapor deposition method and a patterned metal layer processed therefrom is inferior. In particular, in a wet process such as etching (wet processing step using a processing solution) when processing the metal layer into a pattern shape, the problem is that the metal layer is peeled off, or the resin film and the metal in the wet process such as etching described above. When the adhesiveness of the layer is lowered, there is a problem that the so-called dry adhesiveness is lowered, in which the pattern-shaped metal layer is easily peeled off and dropped off in the subsequent handling and post-processing of the conductive film.

Then, in order to solve the said subject, as a result of earnest examination, in the laminated | multilayer film formed by laminating | stacking the resin film (A), the resin layer (B), and the metal layer (C) in this order, the metal layer (C) When the 90 ° peel strength F ₁ at 23 ° C. and 50% RH is 0.5 N / cm or more and the 90 ° peel strength in water of the metal layer (C) is F ₂ , the ratio F by ₂ / _{F 1} is 0.8 or more, and found that the above problems can be solved.

It is important that the 90-degree peel strength F ₁ of the metal layer (C) at 23 ° C. and 50% RH is 0.5 N / cm or more. When F ₁ is 0.5 N / cm or more, it is possible to endure during conveyance in an etching process or the like.

Is not particularly limited maximum _{F 1} is the metal layer (C), the upper limit of _{F 1} of the metal layer (C) is considered to about 20.0N / cm. If F ₁ of the metal layer (C) exceeds 20.0 N / cm, the resin film (A) may be broken inside, and accurate measurement may be difficult.

As a method for setting F ₁ of the metal layer (C) to 0.5 N / cm or more, for example, the above-mentioned underlayer is formed between the resin film (A) and the metal layer (C), or the resin film (C) The method of corona-treating the surface of this can be mentioned.

Furthermore, the metal layer (C), a degree peel strength in water upon the F _2, the ratio F _{2 /} F ₁ it is important that at least 0.8. If the ratio F ₂ / F ₁ is 0.8 or more, the pattern-shaped metal layer is not peeled off or dropped during the etching process and in the subsequent steps. Therefore, the ratio F ₂ / F ₁ is 0.8 or more. It is important to.

The upper limit of the ratio F ₂ / F ₁ is not particularly limited, but the strength hardly increases due to the influence of water, and about 1.2 is considered the limit even when taking measurement errors into consideration. The ratio F ₂ / F ₁ is preferably as large as possible, and in reality, the ratio F ₂ / F ₁ is preferably 0.8 to 1.2.

A resin layer (B) is a layer which has acrylic resin as a main component. Here, the resin layer (B) is mainly composed of an acrylic resin. When the total component of the resin layer (B) is 100% by mass, the resin layer (B) contains 50% by mass of the acrylic resin. This means that the content is 100% by mass or less.

Here, in order to set the ratio F ₂ / F ₁ to 0.8 or more, a method of adjusting the composition of the resin layer (B) is preferable. And to the ratio F _{2 /} F ₁ of 0.8 or more, the resin layer (B) is preferably composed mainly of acrylic resin (B) having a urethane bond.

  Here, the resin layer (B) is mainly composed of an acrylic resin (B) having a urethane bond. When the total component of the resin layer (B) is 100% by mass, the resin layer (B) It means that 50 mass% or more and 100 mass% or less of acrylic resin (B) which has a urethane bond is included.

  The acrylic resin (B) having a urethane bond means a resin whose main skeleton is acrylic acid having a urethane bond or methacrylic acid having a urethane bond. As the acrylic resin (B) having a urethane bond, at least one selected from the group consisting of an alkyl methacrylate and a hydroxyalkyl methacrylate copolymer, acrylic acid and alkyl acrylate (C = 1 to 8), and Suitable examples include a copolymer with at least one selected from the group consisting of alkyl methacrylate (C = 1 to 12) and hydroxyalkyl methacrylate (C = 2, 3).

Here, the acrylic resin (B) having a urethane bond is preferably an acrylic resin obtained by reacting an acrylic resin (b) having a hydroxyl group with an isocyanate compound. The acrylic resin (b) having a hydroxyl group is preferably an acrylic resin having three or more hydroxyl groups, and the acrylic resin (b) having such a hydroxyl group is generally called a polyol. Moreover, the isocyanate compound used here is used as a curing agent.

Examples of the acrylic resin (b) having a hydroxyl group, which is suitably used for producing the acrylic resin (B) having a urethane bond, include an acrylic polyol, a polyester polyol, and a polyether polyol. Acrylic polyol which is a suitable raw material for obtaining an acrylic resin (B) having properties can be suitably used as the acrylic resin (b) having a hydroxyl group.

  As an isocyanate compound suitably used for producing an acrylic resin (B) having a urethane bond, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), IPDI (isophorone diisocyanate), HDI (hexamethylene diisocyanate) In order to obtain an acrylic resin (B) having a urethane bond, it is preferable to use HDI (hexamethylene diisocyanate) as the isocyanate compound.

The acrylic resin (B) having a urethane bond is preferably an acrylic resin obtained by reacting an acrylic resin (b) having a hydroxyl group with an isocyanate compound. The acrylic resin (b) having a glass transition temperature is preferably 30 ° C. or higher and 80 ° C. or lower. When the glass transition point of the acrylic resin (b) having a hydroxyl group is less than 30 ° C., the resulting acrylic resin (B) having a urethane bond is likely to have insufficient water resistance, and swells in a wet process such as etching. There are things to do. On the other hand, when the glass transition point exceeds 80 ° C., the acrylic resin (B) having a urethane bond is poorly soluble in a solvent and tends to cause defects such as coating streaks when applied, and the appearance after drying. The quality tends to deteriorate.

The thickness of the resin layer (B) is preferably 0.05 to 5 μm. When the thickness of the resin layer (B) is less than 0.05 μm, the adhesion with the metal layer (C) may be weakened. On the other hand, if the thickness of the resin layer (B) exceeds 5 μm, the surface of the resin layer (B) itself is liable to crack, and even in this case, the adhesion may be weakened. Also, economically, when the thickness of the resin layer (B) exceeds 5 μm, the cost may increase.

  The thickness of the metal layer (C) is preferably 0.05 to 10 μm. When the thickness of the metal layer (C) is less than 0.05 μm, the electric resistance when the circuit is formed becomes high, and the surface area of the usable circuit board may be limited. Further, when the thickness of the metal layer (C) is less than 0.05 μm, adhesion failure such as peeling during a wet process such as etching may occur. On the other hand, when the thickness of the metal layer (C) is larger than 5 μm, the productivity is lowered due to a decrease in the formation speed of the metal layer and an increase in the etching time during processing to the pattern shape, and also to a high definition pattern shape. It is disadvantageous in the formation of. Also, if the thickness of the metal layer is greater than 5 μm, air bubbles may be mixed when pasting via an adhesive or the like, resulting in a decrease in transparency, or the formation of a functional layer directly on the patterned metal layer. When this is done, there may be inconveniences such as poor coatability and inability to obtain a smooth coated surface.

The metal layer (C) in the laminated film of the present invention preferably has a pattern shape. In this invention, it is invention of the laminated | multilayer film suitable for formation of the electrode and circuit which formed the complicated pattern shape into the film. Therefore, the metal layer (C) can be suitably used for an electrode or a circuit finally by making the pattern shape. Here, the pattern shape is not particularly limited, but a mesh shape and a stripe shape are preferable. As a method for forming the metal layer (C) into a pattern shape, a photoresist-etching method or the like can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In addition, the evaluation method of each sample produced by the present Example is shown below.

(1) Cut out the cross section of the prepared sample with a thickness measurement microtome of the resin layer (B) and metal layer (C), and cut the cross section into a field emission scanning electron microscope (JSM-6700F, JEOL Ltd., Acceleration) Observation was performed at a voltage of 10 kV and an observation magnification of 20,000 times, and the thicknesses of the resin layer and the metal layer were measured. The measurement is performed by measuring five arbitrary points from one 20 cm × 20 cm sample and averaging.

(2) Measurement of 90 degree peel strength F _{1 As} a sample, a laminated film of the present invention was cut into a width of 50 mm and a length of 100 mm, and Nichiban Clear Line Tape No. Five patterns of 557 (tape width 2 mm) were attached to the entire length in the length direction of the laminated film at intervals of 2 mm in the width direction to make a pattern mask for pulling. Further, the laminated film provided with the pattern mask was immersed in a 30% by weight ferrous chloride aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, etched, washed with water, dried, and the pattern mask was peeled off to obtain a sample. .

A tensile tester (peeling tester) conforming to JIS B 7721 (2009) is equipped with a gripping tool for holding the sample horizontally and making the pulling direction of the sample vertical, and the peeling angle is 90. The sample was fixed to the gripping tool with a double-sided tape # 500 made of Nitto, and the metal layer alone was partially peeled off with tweezers, and the sample was fixed to the load cell with a clip and pulled up and measured. Specifically, Tensilon manufactured by Orientech Co., Ltd. was used, and the peeling rate was 30 mm / min and the measurement length was 50 mm. Is using the average intensity in the measured value, the mean value of 5 times the measured value was defined as F _1.

(3) Preparation of 90-degree measurement sample peel strength F ₂ in water, the measuring device using the same method as 90 degrees measurement of peel strength F ₁ of the aforementioned (2).

After fixing the sample with a double-sided tape # 500 made by Nitto Co., Ltd. to a holding tool for holding the sample horizontally and pulling up the sample in the vertical direction, the entire sample is fixed using a polyethylene foam plate. A bank with a height of 2 mm was created to fill it with water. In this state, the interface at which the metal layer peels becomes water. In this state, the measurement was allowed to stand for 2 minutes. Above (1) Similarly, using an average intensity in the measured value, the mean value of 5 times measurements was F _2.

(4) Line loss of pattern, line chipping A resist layer is applied and formed on the surface of the metal layer (C), and the resist layer is exposed and developed through a line pattern mask having a line width of 5 μm and a pitch of 30 μm, and then etched. Processing was performed, and finally the resist was peeled and removed to produce a laminated film in which the metal layer (C) had a pattern shape. A laminated film in which the metal layer (C) has a pattern shape is cut into a width of 50 mm and a length of 50 mm, the pattern lines are observed with an optical microscope at a magnification of 500 times, and there are no omissions or missing lines. When there was a dropout or a line missing even at one place, it was judged as x.

(5) Glass transition temperature (Tg) of acrylic resin
The glass transition temperature refers to the glass transition temperature (Tg) in the general definition of a polymer. 15g of acrylic resin paint is weighed in a glass petri dish, dried in an oven at 120 ° C to remove non-volatile content, 1g is weighed and placed in an aluminum pan, and a thermal differential scanning calorimeter (DSC) manufactured by PerkinElmer Co., Ltd. And measured at a heating rate of 10 ° C./min.

Example 1
A PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  On one surface side of the resin film (A), an acrylic resin (trade name: Cotax (registered trademark) LH404, manufactured by Toray Fine Chemical Co., Ltd.) as the acrylic resin (b) having a hydroxyl group, a glass transition point [hereinafter referred to as Tg. 40 ° C) 3.5 g of isocyanate (type HX) manufactured by Nippon Polyurethane Co., Ltd. was added and diluted with MEK 2.95 g and MIBK 2.95 g. It applied | coated with No. 10 and it dried at 120 degreeC for 1 minute using the hot air oven, and formed the resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.6 N / cm, the 90 degree peel strength F ₂ in water was 1.5 N / cm, and F ₂ / F ₁ was 0.9. There was no missing line or missing line, and the judgment was good.

(Example 2)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  On one side of the resin film (A), acrylic resin (trade name: Cotax (registered trademark) LH404, Tg = 40 ° C.) 3.6 g produced by Toray Fine Chemical Co., Ltd. as an acrylic resin (b) having a hydroxyl group. To this was added 1.1 g of isocyanate (type HL) manufactured by Nippon Polyurethane Co., Ltd., and a 10% solid content paint diluted with 2.65 g of MEK and 2.65 g of MIBK was applied with a metalling bar number of 10 and heated in a hot air oven. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 1.5 N / cm, and F ₂ / F ₁ was 1.0. There was no missing line or missing line, and the judgment was good.

(Example 3)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  On one side of the resin film (A), an acrylic resin (b) made of Toray Fine Chemical Co., Ltd. (trade name: Cotax (registered trademark) LH613, Tg = 75 ° C.) 3.9 g as an acrylic resin (b) having a hydroxyl group. To this, 0.5 g of isocyanate (type HX) manufactured by Nippon Polyurethane Co., Ltd. was added, and a paint with a solid content of 10% by weight diluted with 2.8 g of MEK and 2.8 g of MIBK was applied with a metalling bar number of 10 and heated in a hot air oven. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing nickel (undercoat layer) with a thickness of 10 nm by a batch sputtering apparatus, copper was deposited by a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 1.4 N / cm, and F ₂ / F ₁ was 0.9. There was no missing line or missing line, and the judgment was good.

Example 4
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  Acrylic resin (trade name: Cotax (registered trademark) LH644, Tg = 48 ° C.) 3.5 g as an acrylic resin (b) having a hydroxyl group on one surface side of the resin film (A) To this, 0.3 g of isocyanate (type HL) manufactured by Nippon Polyurethane Co., Ltd. was added, and a 10% by weight solid paint diluted with 3.1 g of MEK and 3.1 g of MIBK was applied with a metalling bar number of 10 and heated in a hot air oven. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing nickel (undercoat layer) with a thickness of 10 nm by a batch sputtering apparatus, copper was deposited by a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 1.5 N / cm, and F ₂ / F ₁ was 1.0. There was no missing line or missing line, and the judgment was good.

(Example 5)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  Acrylic resin (trade name: Cotax (registered trademark) LH644, Tg = 48 ° C.) 3.5 g as an acrylic resin (b) having a hydroxyl group on one surface side of the resin film (A) To this, 0.3 g of isocyanate (type HL) manufactured by Nippon Polyurethane Co., Ltd. was added, and a 10% by weight solid paint diluted with 3.1 g of MEK and 3.1 g of MIBK was applied with a metalling bar number of 10 and heated in a hot air oven. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 30 seconds.

When the thickness of each layer was measured, the thickness of the resin layer (B) was 2 μm, and the thickness of the metal layer (C) was 0.5 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 1.5 N / cm, and F ₂ / F ₁ was 1.0. There was no missing line or missing line, and the judgment was good.

(Example 6)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  Acrylic resin (trade name: Cotax (registered trademark) LH644, Tg = 48 ° C.) 3.5 g as an acrylic resin (b) having a hydroxyl group on one surface side of the resin film (A) Add 0.3 g of isocyanate (type HL) manufactured by Nippon Polyurethane Co., Ltd., and apply a 10% solid content paint diluted with 3.1 g of MEK and 3.1 g of MIBK in No. 2 of the metal ring bar. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the thickness of each layer was measured, the thickness of the resin layer (B) was 0.5 μm, and the thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.6 N / cm, the 90 degree peel strength F ₂ in water was 1.3 N / cm, and F ₂ / F ₁ was 0.8. There was no missing line or missing line, and the judgment was good.

(Example 7)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  Acrylic resin (trade name: Cotax (registered trademark) LH644, Tg = 48 ° C.) 3.5 g as an acrylic resin (b) having a hydroxyl group on one surface side of the resin film (A) Add 0.3 g of isocyanate (type HL) manufactured by Nippon Polyurethane Co., Ltd., and apply a 10% solid content paint diluted with 3.1 g of MEK and 3.1 g of MIBK in No. 2 of the metal ring bar. Was dried at 120 ° C. for 1 minute to obtain a resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. In this case, the ultimate vacuum was 0.02 Pa, 10 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 8 minutes.

When the thickness of each layer was measured, the thickness of the resin layer (B) was 0.5 μm, and the thickness of the metal layer (C) was 5 μm. The 90 degree peel strength F ₁ was 2.0 N / cm, the 90 degree peel strength F ₂ in water was 2.0 N / cm, and F ₂ / F ₁ was 1.0. There was no missing line or missing line, and the judgment was good.

(Example 8)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  On one side of the resin film (A), an acrylic resin (trade name: Cotax (registered trademark) LH635, Tg = 85 ° C.) (3.0 g) manufactured by Toray Fine Chemical Co., Ltd. Type HL) 2.0 g, and a 10% solid content paint diluted with 2.5 g MEK and 2.5 g MIBK is applied with a metalling bar number 10 and dried at 120 ° C. for 1 minute using a hot air oven. Resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 1.5 N / cm, and F ₂ / F ₁ was 1.0. There was no line dropout or line missing, and the judgment was “good”, but streaks were seen in the coating appearance.

(Comparative Example 1)
A PET film (trade name: Lumirror (registered trademark) T60, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  After 10 nm of nickel was applied to one surface side of the resin film (A) with a batch sputtering apparatus, copper was evaporated with a batch type evaporation apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the thickness of each layer was measured, the thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 0.3 N / cm, the 90 degree peel strength F ₂ in water was 0.1 N / cm, and F ₂ / F ₁ was 0.3. Line dropping and line missing frequently occurred, and the judgment was x.


(Comparative Example 2)
In the same manner as in Example 1, a PET film (trade name: Lumirror (registered trademark) U48, thickness: 100 μm) manufactured by Toray Industries, Inc. was used as the resin film (A). This was cut into a 100 mm × 100 mm square and used.

  To one side of the resin film (A), 3.0 g of acrylic resin (trade name: Cotax (registered trademark) LH615, Tg = 14 ° C.) manufactured by Toray Fine Chemical Co., Ltd., isocyanate (manufactured by Nippon Polyurethane Co., Ltd.) Type HL) 2.0 g, and a 10% solid content paint diluted with 2.5 g MEK and 2.5 g MIBK is applied with a metalling bar number 10 and dried at 120 ° C. for 1 minute using a hot air oven. Resin layer (B).

  Next, after depositing 10 nm of nickel (underlayer) with a batch sputtering apparatus, copper was deposited with a batch type deposition apparatus. At that time, the ultimate vacuum was 0.02 Pa, 5 g of copper was placed on a 0.3 mm thick tungsten boat, and vapor deposition was performed at a current of 200 A for 3 minutes.

When the film thickness of each layer was measured, the film thickness of the resin layer (B) was 2 μm, and the film thickness of the metal layer (C) was 2 μm. The 90 degree peel strength F ₁ was 1.5 N / cm, the 90 degree peel strength F ₂ in water was 0.5 N / cm, and F ₂ / F ₁ was 0.3. There were many missing lines and missing lines, and the judgment was x.

  In the table, a case where there was no problem in the appearance of application was indicated as “◯”.

  In the present invention, when a metal film is formed on a resin film and etched to form an electrode or a circuit, defects such as line dropout or line chipping in a wet process step such as etching are prevented, and a high-definition pattern is produced at low cost. Provided is a laminated film suitable for a circuit which can obtain a shape and has improved adhesion between a resin film as a base material and a patterned metal layer. Although it is preferable to use for the processing method to the pattern shape of an electrode or a circuit, the application range is not restricted to these.

1. Resin layer (B)
2. Metal layer (C)
3. Resin film (A)

Claims (6)

A laminated film having a resin film (A), a resin layer (B), and a metal layer (C) in this order,
Metal layer (C), 23 ° C., and 90 ° peel strength _{F 1} under 50% RH is 0.5 N / cm or more, the metal layer (C), a 90-degree peel strength in water and _{F 2} A laminated film, wherein the ratio F ₂ / F ₁ is 0.8 or more.   The laminated film according to claim 1, wherein the resin layer (B) contains an acrylic resin (B) having a urethane bond as a main component. The acrylic resin (B) having a urethane bond is an acrylic resin obtained by reacting an acrylic resin (b) having a hydroxyl group with an isocyanate compound,
The laminated film according to claim 2, wherein the acrylic resin (b) having a hydroxyl group has a glass transition temperature of 30 ° C or higher and 80 ° C or lower.   The laminated film according to claim 1, wherein the resin layer (B) has a thickness of 0.05 to 5 μm.   The laminated film according to any one of claims 1 to 4, wherein the metal layer (C) has a thickness of 0.05 to 10 µm.   The laminated film according to any one of claims 1 to 5, wherein the metal layer (C) has a pattern shape.

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