TW201637852A - Double-sided metal laminated film - Google Patents

Abstract

Provided is a double-sided metal laminated film in which metal-layer adhesion and metal-layer patterning are good. The present invention is a double-sided metal laminated film which has, on both surfaces of a polyester film, a coating layer that is formed from a coating liquid containing a quaternary ammonium salt group-containing compound, a poly(ethylene glycol)-containing acrylate polymer, and a crosslinking agent, and in which a metal layer is laminated on each of the coating layers.

Description

Double-sided metal laminated film

The invention relates to a double-sided metal laminated film for laminating a patterned metal layer, and further relates to a good adhesion to a metal layer, a patterning of a metal layer and a shape of a pattern, and is particularly suitable for A film of a flexible double-sided circuit board or a constituent member for a touch panel (for example, a conductive film).

Previous polyesters have been widely used in various fields due to their mechanical properties, optical properties, dimensional stability, and the like. One of them is for example a flexible substrate.

In recent years, miniaturization, thinning, and light weight of electronic devices represented by televisions, mobile phones, notebook computers, digital cameras, and game consoles have been rapidly promoted. Therefore, even small materials are required for these materials. It is also possible to accommodate materials having high density and high performance.

A flexible double-sided printed wiring board having excellent bending resistance in order to widely use a thin type that can be folded into a narrow space.

But with the need for further high density, relative to folding A flexible double-sided printed wiring board (flexible circuit board) used for a movable portion such as a mobile phone or a folding type mobile phone is also required to have a further narrow pitch and excellent flexibility. Since the structure of the conventional flexible double-sided printed wiring board has a problem that it is broken after being used for a long period of time in the case of multilayering, it is insufficient for applications requiring high bending resistance.

Therefore, a method for achieving high bending resistance has been examined. For example, it is necessary to thin the flexible double-sided printed wiring board itself, for example, the thickness of the insulating film is 20 μm or less.

In addition, the shape of the metal layer (for example, a lattice shape) is deformed due to the shrinkage characteristics of the properties of the polyester film, and the problem of response (reaction) cannot be performed as a wiring substrate. Therefore, a high response is required with respect to the wiring board. The use is insufficient.

Therefore, a method for realizing the heightening of the wiring board has been reviewed, for example, to prevent pattern deformation of the flexible double-sided printed wiring board.

In the configuration of the flexible double-sided printed wiring board, for example, Patent Document 1 discloses a double-sided metal laminated film in which a three-layer metal laminated film structure is formed by laminating a copper foil with an adhesive.

However, in the three-layer metal laminated film structure, in order to obtain a desired wiring pattern, the etching is not only perpendicular to the direction of the substrate surface, but also the planar direction (side wall surface) needs to be etched to form side etching, so the wiring portion tends to be easily inclined. The cross-sectional shape is a type with a wide end, and as a result, there is a problem that it is difficult to narrow the wiring pattern. Further, in this configuration, the surface of the insulating film is bonded to the copper foil via the adhesive layer, so that the thickness of the conductive film is limited in the presence of the copper foil.

Relative to this mainstream, the proposal is flexible two-sided printing In the wiring substrate material, a double-sided metal laminated film of a two-layer metal laminated film structure in which a copper film layer for a conductor layer is directly formed by a dry plating method or a wet plating method without using an adhesive is used.

In the method for forming a two-layer metal laminated film, as described in Patent Document 2, a copper film layer having a uniform film thickness is formed on the insulating film by an electroplating method. In the method, before the copper coating layer is formed by electroplating, a dry plating method such as a vacuum deposition method, a sputtering method, or an ion plating method is used to form a certain thickness on the insulating film, for example, a chromium of about 50 Å to 200 Å. The underlying metal layer formed of a metal other than copper such as chromium oxide or nickel is formed by a method of forming a thin copper layer and an electroless copper plating film by a dry plating method and an electroless plating method in sequence.

However, in the two-layered metal laminate film used for the material of the flexible double-sided printed wiring board in Patent Document 3, the adhesion between the insulating film and the underlying metal layer is insufficient. Therefore, it is required that the underlayer between the insulating film and the metal layer has good adhesion with respect to the insulating film and also has good adhesion with respect to the metal layer laminated above the underlayer.

For example, the process of laminating the metal layer by sputtering, and the heating process after patterning the metal layer after lamination, increases the thermal damage to the film surface of the polyester film, and tends to precipitate oligomers from the film. (mainly a cyclic trimer), and therefore, a device for causing contamination and a film surface protrusion due to precipitation of oligomers on the surface of the film.

Further, in recent years, the high-performance system of the final member has been designed such that the width of the pattern is narrower and the pattern of the metal laminated film is slim.

The polyester film substrate imparts slipperiness for the main purpose To prevent injury in each step, particles are generally added. When a large amount of particles are added to improve the surface roughness of the polyester film substrate, although the rationality of processing the substrate can be improved, when a particle agglomerate exists in the pattern portion of the metal laminated film, a metal laminated film is frequently generated. The pattern is bad.

When no particles are added to the polyester substrate, the film is completely scratched when the film passes through the roll path of each step, so that the patterning failure of the metal laminated film tends to occur frequently, and it is extremely difficult to process into a good metal lamination. film.

In addition, in recent years, high-performance wiring boards having good responsiveness to wiring boards have been designed in accordance with the high performance of the final members.

The polyester film substrate has a shrinkage property which shrinks after heating. The difference in shrinkage ratio (ΔS) between the film running direction (MD) and the direction orthogonal thereto (TD) causes the shape of the patterned metal layer to be deformed, which tends to lower the response of the wiring substrate, so that it cannot be produced. A highly sensitive wiring substrate is extremely difficult to process into a good patterned metal laminate film.

Prior technical literature Patent literature

Patent Document 1: JP-A-6-132628

Patent Document 2: JP-A-8-139448

Patent Document 3: Japanese Patent Publication No. 6-120630

Patent Document 4: JP-A-2014-53410

Summary of invention

In view of the above, the object of the present invention is to provide a good adhesion to a metal layer, and a process of laminating a metal film during lamination and laminating a metal layer after lamination. When the heat treatment is carried out at a temperature of °C or 180 °C, the precipitation of the oligomer can be suppressed, and the shrinkage ratio after the film running direction (MD) and the direction orthogonal thereto (TD) are heated at 150 ° C for 90 minutes can be suppressed, even if it is used. In the type of the wiring substrate which is designed to have a narrower pattern width, a thinned pattern of the metal laminated film, and a high-sensitivity wiring substrate designed to respond to the wiring substrate, patterning failure does not occur. And a patterned metal laminate film which is defective due to deformation of the shape of the patterned metal layer.

In view of the above facts, the present inventors have intensively reviewed and found that a polyester film having a specific coating layer as a constituent member can easily solve the above problems, and the present invention has been completed.

That is, the gist of the present invention is a two-sided metal laminate film characterized in that the polyester film has a compound containing a quaternary ammonium salt-containing compound, a polyethylene glycol-containing acrylate polymer, and a crosslinking agent on both sides of the polyester film. A coating layer formed by the coating liquid, and each of the coating layers is laminated with a metal layer.

According to the double-sided metal laminate film of the present invention, even after the severe heat treatment step of heating the film for a long time under a high temperature environment such as 150 ° C, 90 minutes or 180 ° C, 60 minutes, the precipitation of the oligomer can be prevented as much as possible. The film has a turbidity, has a good adhesion between the polyester film and the coating layer, and the adhesion between the metal layer and the coating layer, and provides a patterning and thinning of the metal laminate film even when used. When the pattern width is narrower and the design type is not good, the patterning failure is not good, and when the circuit board is designed to be highly sensitive and the circuit board is designed to have high sensitivity, The double-sided metal laminated film which is inconvenient due to the deformation of the shape of the patterned metal layer is, for example, a flexible double-sided circuit board or a constituent member for a touch panel (for example, a conductive film), and thus the industrial Sexual value is very high.

Type of implementation of the invention

First, the polyester film will be explained. The polyester film of the present invention may be composed of a single layer or a plurality of layers, and the two or three layers may be formed without any particular limitation, and may be four or more layers.

The polyester is obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic diol. The aromatic dicarboxylic acid is, for example, terephthalic acid or 2,6-naphthalenedicarboxylic acid, and the aliphatic diol is, for example, ethylene glycol, diethylene glycol or 1,4-cyclohexanedimethanol. Representative polyesters such as polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like.

Also, the polyester may be a homopolyester or a copolymerized polyester. Copolymerization In the case of polyester, a copolymer containing a third component of 30 mol% or less is used. Copolymerized polyester dicarboxylic acid components such as isophthalic acid, citric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and oxycarboxylic acid (for example, P-oxygen One or more of a benzoic acid or the like, and a diol component such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexane dimethanol neopentyl glycol or the like More than one species.

In order to suppress the precipitation of the oligomer in the multilayer polyester film, it is preferred to use a titanium compound (Ti) and a phosphorus compound (P), and the content of the compound preferably satisfies the following formulas (1) and (2).

0<Ti≦20...(1)

0≦P≦300...(2)

(In the above formula, Ti is the amount of titanium element (ppm) in the multilayer polyester film, and P is the amount of phosphorus element (ppm)).

Ti is more preferably in the range of 2 to 10 ppm. When Ti exceeds the upper limit of the above formula (1), the oligomer is produced as a by-product in the step of melt-extruding the polyester, and a film having less oligomers and high transparency cannot be obtained. Moreover, it is difficult to respond to the use of optical applications, etc., especially the color of a coating film.

Further, P is preferably from 5 to 200 ppm, particularly preferably from 0 to 100 ppm. When P exceeds the upper limit of the above formula (2), gelation occurs during the production of the polyester to form a foreign matter, and the quality of the film is lowered. Therefore, it is difficult to cope with an inspection step that requires optical evaluation, such as the use of a touch panel.

By simultaneously satisfying the above formulas (1) and (2), a more remarkable effect can be obtained with respect to reducing the oligomer content in the multilayer polyester film.

Further, in the layer containing the titanium compound and the phosphorus compound, In essence, it is preferably not contained in the antimony element, and is usually 10 ppm or less, preferably 5 ppm or less, and most preferably substantially not contained, that is, 1 ppm or less. When the amount of the lanthanum element is too large, it is reduced or aggregated by the above-mentioned phosphorus compound during melt extrusion, which may cause foreign matter, or the film may be blackened and the transparency may be insufficient.

The polyester constituting the layer containing the titanium compound and the phosphorus compound in the above range may be obtained by melt polymerization, and when the raw material obtained by solid phase polymerization of the fragmented polyester is used after melt polymerization, the raw material may be reduced. It is preferred to contain the amount of the oligomer.

The amount of the oligomer contained in the layer containing the titanium compound and the phosphorus compound in the above range is generally 0.7% by weight or less, preferably 0.5% by weight or less.

The present invention may be a film having a structure obtained by co-extruding a polyester having a small oligomer content on at least one side surface of a layer formed of a polyester having a general oligomer content. When this structure is provided, the effect of suppressing the precipitation of the oligomer obtained by the present invention can be exhibited to a high degree.

The maximum roughness (St) of the surface of the film is preferably such that each surface has a range of 10 to 100 nm, more preferably 10 to 50 nm. When the maximum roughness value (St) is less than 10 nm, the surface of the film is too smooth, and the tendency is often caused to be injured in the manufacturing process of the multilayer polyester film. Further, when the thickness exceeds 100 nm, the pattern is formed on the transparent conductive film, and particularly, the wiring width is 4 μm or less, and the pattern portion is extremely fine, and the frequency of occurrence of wiring breakage is increased in the crystallization step of the transparent conductive layer. Further, when the laminate is formed by laminating a coating film with an adhesive, the turbidity of the laminate is greatly improved, so that it is not suitable as an optical member from the viewpoint of optical properties or visibility.

In the outer layer composed of a plurality of layers in the present invention, the main purpose is to impart slipperiness and prevent damage in each step, and it is preferred to add particles having an average particle diameter of 0.1 to 0.6 μm.

The particles to be added are preferably a single species, and may be particles capable of imparting slipperiness, and specific examples thereof include cerium oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, and kaolin. Particles such as alumina and titania. In addition, the heat-resistant organic particles described in JP-A-59-5216, JP-A-59-217755, and the like can be used.

Other heat resistant organic particles are, for example, a thermosetting urea resin, a thermosetting phenol resin, a thermosetting epoxy resin, a benzoguanamine resin, or the like. Further, it is possible to precipitate and finely disperse the precipitated particles by using a metal compound such as a part of a catalyst in the polyester production process.

Further, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, and a flat shape can be used. Further, the hardness, specific gravity, color, and the like are not particularly limited.

The content of the particles in the other two outer layers is generally from 0.05 to 1.0% by weight, preferably from 0.05 to 0.5% by weight. When the particle content is less than 0.05% by weight, the slipperiness of the film will be insufficient, and as a result, appearance defects such as injury may occur during film processing. Further, when the addition exceeds 1.0% by weight, the transparency of the film will be insufficient.

Further, in the polyester layer constituting the outermost layer of the multilayer polyester film, alumina particles are preferably used in order to prevent injury and impart slipperiness. When the average particle diameter of alumina particles exceeds the above range, there will be a lack of prevention The effect of injury and slipperiness.

Specific examples of the alumina particles include γ-type, δ-type alumina, etc., which are produced by hydrolyzing the aluminum chloride anhydride by flame.

The method of adding the particles to the polyester is not particularly limited, and a previously known method can be employed. For example, it is preferably added at any stage of the production of the polyester constituting each layer, and it is preferably added after completion of the esterification or transesterification reaction.

Further, a method of mixing a particle slurry of ethylene glycol or water or the like with a polyester raw material by using a kneading extruder having a vent opening, or blending dry particles with a polyester raw material by using a kneading extruder can be used. The method is carried out.

Further, in the polyester film, in addition to the above particles, a previously known ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a dye, a pigment or the like may be added as necessary.

The thickness of the polyester film is not particularly limited insofar as it can be formed into a film, and is generally in the range of 9 to 80 μm.

Next, a production example of the polyester film will be specifically described, but it is not limited to the following production examples.

First, it is preferred to use a chill roll to cool and solidify the melted sheet extruded from the die using the polyester raw material previously described to obtain an unstretched sheet. In this case, in order to improve the planarity of the sheet, it is preferred to improve the adhesion between the sheet and the rotary cooling drum, and it is preferable to apply electrostatic sealing and/or liquid coating.

Next, the biaxial direction of the resulting unstretched film is extended. In this case, the unidirectional direction of the unextended sheet is first extended by a roll or tenter type stretching machine. The extension temperature is generally 70 to 120 ° C, preferably 80 to 110 °C, the stretching ratio is generally 2.5 to 7 times, preferably 3.0 to 6 times. Next, the extension temperature orthogonal to the first direction of extension is 70 to 170 ° C, and the stretching ratio is generally 3.0 to 7 times, preferably 3.5 to 6 times. Then, the heat treatment is continued at a temperature of 180 to 270 ° C under tension or within 30% to obtain a biaxial alignment film.

The above extension may also be carried out by a method of extending in one direction in two or more stages. In this case, it is preferable that the stretching ratios in the final two directions are each in the above range.

A simultaneous biaxial stretching method can also be used for the production of the polyester film. At the same time, the biaxial stretching method is: in the method of controlling the unstretched sheet at 70 to 120 ° C, preferably 80 to 110 ° C while extending the mechanical direction and the width direction, the stretching ratio is 4 to 50 times the area magnification. Preferably, it is 7 to 35 times, more preferably 10 to 25 times. Next, heat treatment is carried out at a temperature of 170 to 250 ° C under tension or within a relaxation of 30% to obtain an extended alignment film. The simultaneous biaxial stretching device adopting the above extension mode may adopt a previously known extension manner such as a spiral method, a pantograph method, a linear driving method, or the like.

In the present invention, in order to impart adhesiveness, antistatic property, slidability, mold release property and the like to the film of the multilayered polyester film during and/or after the stretching, in the scope of the present invention, A surface treatment such as corona treatment is applied to the surface of the film.

Next, the coating layer forming the double-coated film will be described. The coating layer of the present invention may be coated by a wire coating method when the film surface is treated during the film forming process of the polyester film, or may be applied after the film is produced. Off-line coating method settings. Since the manufacturing cost can be reduced at the time of film formation and coating at the same time, it is preferable to use a wire coating.

The coating layer may contain a surfactant, an antifoaming agent, a coatability improver, a tackifier, an organic lubricant, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, a pigment, or the like. additive.

The coating layer is required to contain a compound containing a quaternary ammonium salt group in order to reduce the amount of oligomer precipitation which is increased from external heat damage to the coating layer.

The compound having a quaternary ammonium salt group is mainly composed of a main chain in a molecule or a branch having a constituent element having a quaternary ammonium salt group. Specifically, for example, a pyridinium ring, a quaternary compound of an alkylamine, and the copolymerized with acrylic acid or methacrylic acid, a quaternary compound of N-alkylamino acrylamide, vinylbenzyltrimethyl An ammonium salt, a 2-hydroxy 3-methylpropoxypropyltrimethylammonium salt or the like. Again, these may be combined or copolymerized with other binder polymers. Further, the anion for the counter ion of the quaternary ammonium salt is an ion such as a halogen, an alkyl sulfide, an alkyl sulfonate or nitric acid. Among them, the counter ion other than the halogen is particularly preferably excellent in heat resistance.

The compound having a quaternary ammonium salt group is preferably a polymer compound. When the molecular weight is too low, it is easily removed from the coating layer, and the performance is lowered over time, or the coating layer is clogged. Moreover, when the molecular weight is low, the heat stability is poor.

From this point of view, the number average molecular weight of the compound having a quaternary ammonium salt group is generally 1,000 or more, preferably 2,000 or more, more preferably 5,000 or more. However, when the number average molecular weight is too high, the coating liquid is excessively increased. Viscosity is not suitable. From this point of view, the upper limit of the number average molecular weight is preferably 500,000 or less.

Further, these compounds may be used singly or in combination of two or more.

The ratio of the content of the compound containing a quaternary ammonium salt group to the total solid content in the coating liquid for forming the coating layer is generally from 20 to 70% by weight, preferably from 40 to 70% by weight. When it is outside this range, it will be difficult to obtain the desired effect of blocking the oligomer.

Further, in order to ensure that the coating layer has a higher coating property than before, it has good elongation followability in forming the coating layer, and it is necessary to contain a polyethylene glycol-containing acrylate polymer.

Specifically, for example, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol diacrylate (polymerization degree of polyethylene glycol unit is preferably in the range of 4 to 14), polypropylene glycol diacrylate, Polytetramethylene glycol diacrylate, poly(ethylene glycol-tetramethyl glycol) diacrylate, poly(propylene glycol-tetramethyl glycol) diacrylate, polyethylene glycol-polypropylene glycol-polyethylene glycol Acrylate, polypropylene glycol-polybutylene glycol monomethacrylate, methoxy polyethylene glycol monomethacrylate, methoxy polyethylene glycol monoacrylate, octyloxy polyethylene glycol-polypropylene glycol Monomethacrylate, octyloxy polyethylene glycol-polypropylene glycol monoacrylate, lauryloxy polyethylene glycol monomethacrylate, lauryloxy polyethylene glycol monoacrylate, stearoxy polyethylene Polymers such as diol monomethacrylate, stearyloxy polyethylene glycol monoacrylate, propyleneoxy polyethylene glycol monomethacrylate, propylene oxy polyethylene glycol monoacrylate, etc. .

Number average molecule of PEG polymer containing polyethylene glycol The amount is generally 1,000 or more, preferably 2,000 or more, more preferably 5,000 or more. Further, when the number average molecular weight is too high, the viscosity of the coating liquid is excessively increased, which is not preferable. From this point of view, the upper limit of the number average molecular weight is preferably 500,000 or less.

Further, these compounds may be used singly or in combination of two or more. Further, the chain length of the alkyl chain in the polyethylene glycol-containing alkyl acrylate polymer may be, and is not particularly limited, in the range in which it can be polymerized into a polymer.

The ratio of the content of the polyethylene glycol-containing polymer to the total solid content in the coating liquid for forming the coating layer is usually from 5 to 40% by weight, preferably from 20 to 30% by weight. When it exceeds this range, it is not preferable to extend the followability when forming a coating layer.

The quaternary ammonium salt-containing compound and the polyethylene glycol-containing acrylate polymer may be a mixture or a copolymerization, and are not particularly limited as long as the gist of the present invention is not impaired. Further, a previously known production method can be used in the copolymerization.

Further, in order to further improve the durability of the coating layer, a crosslinking agent is used in combination.

Specifically, for example, methylolated or alkylated urea, melamine, guanamine, acrylamide, polyamine compound, epoxy compound, aziridine compound, block polyisocyanate, titanium coupling agent, zirconium aluminum An acid salt coupler, a polycarbodiimide or the like.

Among the crosslinking agents, in particular, in view of the use of the present invention, good coating properties and durability adhesiveness are obtained, and a melamine crosslinking agent is preferred. The melamine crosslinking agent is not particularly limited, and melamine or melamine can also be used. A methylolated melamine derivative obtained by condensation with formaldehyde, a compound obtained by partially or completely etherifying a methylolated melamine with a lower alcohol, and a mixture thereof.

Further, as the melamine crosslinking agent, any one of a condensate formed of a monomer or a polymer of a dimer or more, or a mixture thereof may be used. The lower alcohol used for the above etherification is preferably methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol or the like. Further, an imido-type methylated melamine or a methylol group having an alkoxymethyl group such as an imido group, a methylol group, a methoxymethyl group or a butoxymethyl group having a functional group in one molecule can be used. Type melamine, methylol type methylated melamine, fully alkyl type methylated melamine, and the like. The best one is methylolated melamine. Further, in order to promote thermal hardening of the melamine crosslinking agent, for example, an acidic catalyst such as p-toluenesulfonic acid may be used in combination.

The ratio of the content of the crosslinking agent to the total solid content in the coating liquid for forming the coating layer is usually from 10 to 60% by weight, preferably from 20 to 50% by weight. When it exceeds this range, the durability adhesiveness with respect to the coating layer of a metal layer will be inadequate.

Further, in order to improve the fixing property and the slidability, the coating layer preferably contains particles. Specifically, for example, cerium oxide, aluminum oxide, kaolin, calcium carbonate, titanium oxide, cerium salt, or the like.

The ratio of the content of the particles to the total solid content in the coating liquid for forming the coating layer is usually 0.5 to 10% by weight, preferably 1 to 5% by weight. When the amount added is less than 0.5% by weight, the blocking resistance will be insufficient, and when it exceeds 10% by weight, the transparency of the film will be lowered.

Further, in the range which does not impair the gist of the present invention, if necessary, the coating layer may contain an antifoaming agent, a coating improver, a tackifier, an organic lubricant, an organic polymer particle, an antioxidant, and an ultraviolet absorbing foam. Agents, dyes, etc.

The coating stretching method (wiring coating) is preferably applied to a polyester film by adjusting a coating liquid having a solid content concentration of about 0.1 to 50% by weight after the series of compounds are made into an aqueous solution or a water dispersion. Upper to produce a laminated polyester film.

In addition, in order to improve the dispersibility with respect to water, film-forming property, etc., it is possible to contain a small amount of organic solvent in the coating liquid. An organic solvent such as an aliphatic or alicyclic alcohol such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol or methyl alcohol, propylene glycol, ethylene glycol, diethylene glycol, or the like Glycols, n-butyl cellosolve, ethyl cellosolve, methyl cellosolve, diol derivatives such as propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, ethyl acetate, ethyl acetate An ester such as an ester, a ketone such as methyl ethyl ketone or acetone, or a guanamine such as N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more.

The coating amount (after drying) of the coating layer is usually from 0.005 to 1 g/m ² , preferably from 0.005 to 0.5 g/m ² , more preferably from 0.005 to 0.1 g/m ² . When the coating amount is less than 0.005 g/m ² , the uniformity of the coating thickness is insufficient, and the amount of the oligomer deposited on the surface of the coating layer is increased after the heat treatment. Further, when the coating amount exceeds 1 g/m ² , the slidability or the like is lowered, which is not preferable.

Further, the coating layer may be used in combination with a polyester resin in order to improve the coating appearance, prevent oligomer precipitation, and the like without departing from the gist of the present invention. A binder polymer such as an acrylic resin, a polyurethane resin, or a polyvinyl alcohol.

The coating method of the coating liquid may use a previously known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, spray coating, or the like. . The coating method, such as the "coating method", is an example of the 1979 issue of the bookstore.

When the double-sided metal laminate film of the present invention is used for, for example, a touch panel or the like, it is required to have high transparency even when exposed to a high temperature environment for a long period of time. From this point of view, in order to correspond to a member used as a touch panel, the film turbidity change rate (heat turbidity, ΔH) before and after heat treatment (150 ° C, 90 minutes) is generally 0.5% or less, preferably 0.3% or less. More preferably, it is 0.1% or less. When ΔH exceeds 0.5%, the turbidity of the film is increased to lower the visibility, and it is not preferable to use it for high visibility such as a touch panel. Further, when ΔH is low, it means that the amount of oligomer precipitation is small.

Therefore, the double-sided metal laminate film which satisfies the above characteristic value can be obtained by using a double-faced coating film which satisfies the above characteristic value.

The amount of the oligomer (cyclic trimer) obtained by extracting the surface of the coating layer (single side) by dimethylformamide before and after heat treatment (150 ° C, 90 minutes) of the double-sided metal laminate film of the present invention (OL) is usually 0.5 mg/m ² or less, preferably 0.4 mg/m ² or less. When the OL exceeds 1.0 mg/m ² , in the heat treatment step such as post-processing, for example, a sputtering step, for example, heat treatment for a long period of time in a high-temperature environment such as 180° C. or 60 minutes increases the amount of oligomer deposition. Will reduce the transparency of the film.

Therefore, the double-sided metal laminate film which satisfies the above characteristic value can be obtained by using a double-faced coating film which satisfies the above characteristic value.

In the process of laminating the metal film in the process of laminating the metal film at a temperature of about 150 ° C or about 180 ° C, the oligomer is precipitated, and the pattern width is narrower, and the pattern of the metal layer film is slender. There will be problems such as poor graphics and so on. The inventors of the present invention estimated that the maximum roughness (St) of the outermost surface of the multilayer polyester film substrate constituting the coated film is one of the causes of poor patterning.

The surface roughness (St) of the coating layer before and after the heat treatment of the double-coated film is preferably in the range of 10 to 100 nm, more preferably 10 to 50 nm.

Preferably, the double-sided metal laminate film of the present invention has an absolute value of a shrinkage ratio (ΔS) after heating in a film running direction (MD) and a direction orthogonal thereto (TD) at 150 ° C for 90 minutes. Description.

△S=|SMD-STD|=0.5 or less

(In the above formula, SMD represents the shrinkage ratio (%) in the film running direction, and STD represents the shrinkage ratio (%) in the direction orthogonal to the film running direction).

SMD is generally in the range of 0.2 to 1.5%. The STD is generally in the range of 0.0 to 1.0%.

ΔS is preferably 0.3 or less, more preferably 0.1 or less.

When ΔS exceeds 0.5, the shape of the patterned metal layer is deformed, and the responsiveness of the wiring board tends to be lowered, which makes it difficult to cope with a wiring substrate having high sensitivity.

Further, the double-coated film constituting the double-sided metal laminate film of the present invention is also preferably a shrinkage ratio after the film running direction (MD) and the direction orthogonal thereto (TD) are heated at 150 ° C for 90 minutes. The absolute value of the difference (ΔS) satisfies the following formula.

[Number 1] △S=|SMD-STD|=0.5 or less

(In the above formula, SMD represents the shrinkage ratio (%) in the film running direction, and STD represents the shrinkage ratio (%) in the direction orthogonal to the film running direction).

SMD is generally in the range of 0.2 to 1.5%. The STD is generally in the range of 0.0 to 1.0%.

ΔS is preferably 0.3 or less, more preferably 0.1 or less.

When ΔS exceeds 0.5, the shape of the patterned metal layer is deformed, and the responsiveness of the wiring board tends to be lowered, which makes it difficult to cope with a wiring substrate having high sensitivity.

Therefore, the double-sided metal laminate film which satisfies the above shrinkage property value can be obtained by using a double-faced coating film which satisfies the above shrinkage property value.

Next, a metal layer forming a double-sided metal laminated film will be described. The metal used for the metal layer may be a metal monomer such as gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, indium, or the like, or a nickel-chromium alloy or the like. Metal solid solution (alloy). Among them, the versatility of forming a metal film, the cost, the ease of removal by etching, and the like are preferable, and chromium, nickel, titanium, nickel-chromium alloy, aluminum, zinc, copper-nickel alloy, copper-titanium is preferable. Alloy, gold, silver and copper. More preferably, it is chromium, nickel, titanium, nichrome, aluminum, zinc, gold, silver and copper. The best is copper (including copper oxide). Further, the metal film layer may be a single layer or a multi-layer structure obtained by laminating two or more layers of different metals.

The layer thickness of the metal layer is not particularly limited, but is preferably 5 nm to 500 nm, more preferably 10 nm to 300 nm. When the layer thickness of the metal layer is less than 5 nm, the metal layer is easily cracked. Further, when the layer thickness of the metal layer exceeds 500 nm, it is necessary to form a metal layer for a long period of time, which tends to increase the cost.

The method of forming a metal layer on the coating layer may employ a previously known method. Specifically, it is preferably formed by one or more methods selected from the group consisting of a vapor deposition method, a sputtering method, and an ion plating method, and is particularly preferably formed by a sputtering method. The foregoing methods may be used in combination of two or more kinds, or any one of them may be used alone.

In the vapor deposition method (vacuum vapor deposition method), a support (corresponding to the double-coated film of the present invention) is preferably placed in a vacuum container, and the metal is heated and evaporated to form a metal layer on the coating layer.

Preferably, the sputtering method is carried out by placing a support (corresponding to the double-coated film of the present invention) in a vacuum container, introducing an inert gas such as argon, and applying a DC voltage to cause the ionized inactive gas to strike the target metal. And forming a metal layer on the coating layer by the metal being knocked out.

Preferably, the ion plating method comprises: placing a support (corresponding to the double-coated film of the present invention) into a vacuum container, heating and evaporating the metal in an illuminating discharge environment, and evaporating the metal on the coating layer by ionization A metal layer is formed.

Patterning can be performed using previously known techniques. For example, it is described in JP-A-2014-150118.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but without departing from the scope of the invention. In the examples and comparative examples, "parts" means "parts by weight". Further, the measurement method and evaluation method used in the present invention are as follows.

(1) Method for determining the intrinsic viscosity of polyester:

1g of polyester which removes other polymer components and pigments which are incompatible in polyester, and then added 100ml of a mixed solvent of phenol/tetrachloroethane=50/50 (weight ratio), dissolved and measured at 30 ° C .

(2) Average particle size (d50) and particle size distribution:

A centrifugal precipitation type particle size distribution measuring apparatus SA-CP3 type manufactured by Shimadzu Corporation was used, and the particle size was measured by a precipitation method according to the resistance of Stokes, and the average particle diameter was determined. The particle size distribution was determined by the same method as the average particle diameter. That is, the total particle side of the equivalent spherical distribution is integrated, and the particle size distribution ratio (R) is calculated by the following formula.

(r) = particle size when the particle weight is 25%, the particle size is 75%, and the particle size is 75%.

(3) Method for determination of oligomer content in polyester raw materials:

About 200 mg of the polyester raw material was weighed and dissolved in 2 ml of a mixed solvent of chloroform/HFIP (hexafluoro-2-isopropanol) in a ratio of 3:2. After dissolving, 20 ml of chloroform was added, and 10 ml of methanol was added in a small amount. After the precipitate was removed by filtration, the precipitate was washed with a mixed solvent of chloroform/methanol ratio of 2:1, and the filtrate and the washing liquid were collected, concentrated by an evaporator, and dried. After dissolving the dry solid in 25 ml of DMF (dimethylformamide), the solution was supplied to a liquid chromatograph (manufactured by Shimadzu Corporation: LC-7A) to determine the amount of oligomer in DMF, and then dissolved in chloroform. The amount of the polyester raw material of the /HFIP mixed solvent is divided by this value as the oligomer content (% by weight). The amount of oligomer in DMF is determined by the ratio of the peak area of the standard sample to the peak area of the peak area of the sample (absolute line method).

The standard sample is prepared by properly weighing the pre-treated oligomer (ester cyclic trimer) and dissolving it in DMF which is properly weighed. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg/ml.

Further, the conditions of the liquid chromatography are as follows.

Mobile phase A: acetonitrile

Mobile phase B: 2% aqueous acetic acid solution

Pipe column: MCI GEL ODS 1HU by Mitsubishi Chemical Corporation

Column temperature: 40 ° C

Flow rate: 1ml/min

Inspection wavelength: 254nm

(4) Thickness of laminated polyester layer:

After the film piece was fixed by epoxy resin, it was cut with a thin cutter, and the film profile was observed by a light-transmitting electron microscope photograph. As a result, two interfaces formed from light and dark, which are almost parallel to the film profile, were observed. The distance between the two interfaces and the surface of the film was measured from 10 photographs, and the average value was used as the laminate thickness.

(5) Quantification of metal elements and phosphorus elements in polyester film:

The amount of the element in the film was measured by a single film FP method under the conditions shown in Table 1 below using a fluorescent X-ray analyzer (Shimadzu Corporation) "XRF-1500". The test limit is generally 1 Ppm.

(6) Amount of oligomer extracted from the surface of the coating layer of the double-coated film (OL) measurement method:

The film was coated on both sides at 150 ° C for 90 minutes in air first. Thereafter, the film after the heat treatment was adhered as much as possible to the inner surface of the box having an outer opening of 10 cm in length and 3 cm in height to form a box shape. Next, 4 ml of DMF (dimethylformamide) was placed in a box prepared by the above method, and DMF was recovered after standing for 3 minutes. The recovered DMF was supplied to a liquid chromatograph (manufactured by Shimadzu Corporation: LC-7A), and the amount of the oligomer in the DMF was determined, and the film area of the DMF was divided by the value to obtain the amount of oligomer on the surface of the film (mg/m ^{2 ).} ). The amount of oligomer in DMF is determined by the ratio of the peak area of the standard sample to the peak area of the peak area of the sample (absolute line method) (A side).

The opposite side (side B) of the above method was measured, and the amount of oligomer (OL) extracted from the surface of the coating layer was determined.

The standard sample is prepared by properly weighing the pre-treated oligomer (cyclic trimer) and dissolving it in a properly weighed DMF. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg/ml.

Further, the conditions of the liquid chromatography are as follows.

Mobile phase A: acetonitrile

Mobile phase B: 2% aqueous acetic acid solution

Pipe column: MCI GEL ODS 1HU by Mitsubishi Chemical Corporation

Column temperature: 40 ° C

Flow rate: 1ml/min

Inspection wavelength: 254nm

(7) Determination of turbidity (H0) of the coated film on both sides:

According to JIS-K-7136, "HM-150" by Murakami Color Research Institute The film turbidity of the sample film was measured.

(8) Determination of turbidity (H1) of the coated film on both sides after heat treatment:

After the sample film was treated under a certain heat treatment condition (150 ° C, 90 minutes), the film turbidity was measured in the same manner as in (7).

(9) Determination of turbidity change rate (heat turbidity, ΔH) of the coated film on both sides:

The turbidity change rate (heat turbidity, ΔH) of the double-coated film was calculated from the measured values of the items (7) and (8).

△H=(H1)-(H0)

(9) Determination of the maximum surface roughness (St) of the coated film on both sides (before heat treatment):

The surface roughness (St) of the measurement surface of the test material film was measured by the direct phase-detection interference method, that is, the two-beam interference method using the Michelson interference, and the non-contact surface measurement system "Micromap 512 manufactured by Microtel". Further, the measurement wavelength was 530 nm, the object lens system was used 20 times, and the 20-degree field of view was measured. After removing the maximum value and the minimum value in the measurement values after the total measurement of 12 points, the average value of 10 points was used as the surface roughness. (St). The surface roughness (St1) (surface A) of the surface of the film before the heat treatment of the coated film was measured by the above measurement method. The surface roughness (St2) of the opposite side (B side) was measured in the same manner as above.

(11) Determination of the maximum surface roughness (St) of the coated film on both sides (after heat treatment):

The surface roughness (St3) (surface A) of the surface of the film after heat-treating the film at 150 ° C for 90 minutes was measured in the same manner as in the above (10).

The surface roughness (St4) of the opposite side (B side) was measured in the above manner.

(12) Determination of the maximum roughness (St) of the surface of the patterned metal layer:

On the surface of the film coated on both sides of the film, a copper oxide layer having a thickness of 20 nm was formed by reactive sputtering using a sintered material. A patterned photoresist (the finest portion: 20 μm) was applied onto the copper oxide layer, and after drying and hardening, the obtained copper oxide layer was immersed in a 4% aqueous solution of ferric chloride for etching treatment. The resulting patterned copper oxide layer was crystallized by heat treatment at 150 ° C for 90 minutes. The surface roughness (St5) (A surface) of the metal layer region of the obtained patterned copper oxide layer was measured in the same manner as in the above (10).

(13) Determination of the maximum roughness (St) of the surface of the patterned metal layer:

After patterning the opposite side (B side) of (12) with the method of the above (10), the surface roughness (St6) of the metal layer field of the obtained patterned copper oxide layer is measured in the same manner as in the above (10). .

(14) Maximum surface roughness of the field in which the patterned metal layer is not provided (St) Determination:

The surface roughness (st) in the non-metal field of the measurement (12) is the same as the above (10) as the surface roughness (St7) (A surface).

(15) Determination of the maximum surface roughness (St) of the field in which the patterned metal layer is not provided:

The surface roughness (st) in the field of the non-metal layer of the measurement (13) is determined as the surface roughness (St8) (B surface) in the same manner as in the above (10).

(16) Determination of shrinkage ratio (SMD, STD) of two-sided metal laminate film and double-coated film:

The sample film was heat-treated in an oven maintained at a constant temperature (150 ° C) for 90 minutes under no tension, and the length of the sample before and after the measurement was measured by the following formula. Further, MD and TD of the coated film were each measured.

Shrinkage = {(sample length before heat treatment) - (sample length after heat treatment)} / (sample length before heat treatment) × 100

(17) Evaluation of adhesion to metal layer (utility evaluation of utility characteristics):

A 20 nm thick copper oxide layer was formed on the surface of the film coated on both sides by reactive sputtering. A patterned photoresist was applied onto the copper oxide layer, and after drying and coating, the obtained copper oxide layer was immersed in a 4% aqueous solution of ferric chloride, and etching treatment was performed to make the residual copper oxide layer 3 mm wide. By The resulting patterned copper oxide layer was crystallized by heat treatment at 150 ° C for 90 minutes. Next, the "Ezgraph" manufactured by Shimadzu Corporation was used, and the tensile test was carried out in the direction of 90 degrees in accordance with JIS C 5016, and the adhesion force with respect to the metal layer was measured, and the judgment was made based on the following criteria (A side). The measurement is performed on the opposite side (side B) in the same manner as above, and the judgment is made based on the following criteria.

Judgment Benchmark

A: The adhesion is 0.5 N/mm or more, and the adhesion is good (the level of practical no problem)

B: The adhesion is 0.3~0.4N/mm, and the adhesion is normal (the level of problems will be practical)

C: The adhesion is 0.2 N/mm or less, and the adhesion is poor (the level of practical problems)

(18) Evaluation of wiring breakage after patterning of copper layer (evaluation of practical characteristics of heat resistance):

A copper oxide layer having a thickness of 20 nm was formed on the surface of the film coated on both sides by a reactive sputtering method using a sintered material. A photoresist having a linear pattern (the finest portion: 4 μm, 8 μm, 12 μm, 20 μm) was applied onto the copper oxide layer, and after drying and hardening, the obtained copper oxide layer was immersed in a 4% aqueous solution of ferric chloride. Etching treatment. The resulting patterned copper oxide layer was crystallized by heat treatment at 150 ° C for 90 minutes.

Using an optical microscope (a micro-experimental model of the company) No.: VHX-200) Check the 100th finest part of the obtained patterned copper oxide layer at a magnification of 40 times, check whether the copper oxide layer is broken, and evaluate the linearity of the wiring after patterning by the following reference (A surface). Check the opposite side (side B) with the above method, and judge by the following criteria.

Judgment Benchmark

A: Both the A side and the B side confirm that the copper wiring is not broken.

B: Although the copper wiring was not confirmed on the A side and the B side, it was confirmed that the wiring was slightly cracked.

C: Both the A side and the B side confirm that there is one or more broken copper wirings.

(19) Evaluation of the shape (deformation) of the pattern after the copper layer is patterned:

A copper oxide layer having a thickness of 20 nm was formed on the surface of the film on both sides of the film by a reactive sputtering method using a sintered material. A photoresist having a lattice pattern (the finest portion: 4 μm) was applied onto the copper oxide layer, dried and hardened, and the obtained copper oxide layer was immersed in a 4% aqueous solution of ferric chloride for etching treatment. The dimensional change (X, Y) of the lattice pattern (X length = 3.00 mm before heating, Y length = 3.00 mm before heating) before and after the heat treatment at 150 ° C for 90 minutes was observed using a measuring microscope, and then judged by the following The benchmark is judged. Further, the shape deformation of the patterned metal layer is caused by the difference in shrinkage between the MD and the TD of the coated film. Therefore, this assessment only performs an A-side assessment for the sake of simplicity.

(judgment basis)

A: The difference between the X and Y length after heating is 0.01 mm or less (there is almost no dimensional change before and after the heat treatment, and there is no problem in practical use)

B: The difference between the X and Y length after heating exceeds 0.01 mm (there is a dimensional change before and after the heat treatment, and the level of practical problems)

(20) Comprehensive assessment:

In the metal laminated film of each of the two-sided pattern obtained in the examples and the comparative examples, the adhesion to the metal layer, the wiring breakage after the copper oxide layer patterning, and the pattern after the copper layer patterning were completed. After the shape (deformation) is evaluated, a comprehensive evaluation is performed on the basis of the following criteria.

Judgment Benchmark

A: The wire breakage evaluation after the patterning of the copper oxide layer with respect to the metal layer is A (practical problem-free level)

B: At least one of the evaluations of the wiring breakage after the adhesion of the metal layer and the pattern of the copper oxide layer is B (a practical level of problem)

C: at least one of the evaluations of the wiring breakage after the adhesion of the metal layer and the pattern of the copper oxide layer is C (practical problem level)

The polyester film used in the examples and the comparative examples was prepared by the following method.

<Manufacture of polyester> [Manufacturing Method of Polyester (I)]

100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol In order to start the raw material, tetrabutoxy titanate as a catalyst was added and placed in a reactor, and the reaction temperature was 150 ° C, and the reaction temperature was gradually raised while distilling off methanol, and it was 230 after 3 hours. °C. The transesterification reaction was substantially terminated after 4 hours. The reaction mixture was transferred to a polycondensation tank, and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised to 280 ° C from 230 ° C, and the pressure was gradually reduced from normal pressure to a final value of 0.3 mmHg. After the start of the reaction, the reaction force was changed by the reaction vessel, and the reaction was stopped when the ultimate viscosity was equivalent to 0.55. The polymer was discharged under nitrogen pressure to obtain an ultimate viscosity of 0.59 and an oligomer (ester cyclic trimer) content of 0.89 by weight. % polyester (I).

[Method of Manufacturing Polyester (II)]

The polyester (I) was preliminarily crystallized at 160 ° C, and solid phase polymerization was carried out under a nitrogen atmosphere at a temperature of 220 ° C to obtain a polyester having an ultimate viscosity of 0.72 and an oligomer (ester cyclic trimer) content of 0.46 wt%. (II).

[Method of Manufacturing Polyester (III)]

100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol were used as starting materials, and magnesium acetate tetrahydrate as a catalyst was added and placed in a reactor, and the reaction temperature was 150 ° C, and the mixture was distilled off. The reaction temperature was gradually raised while methanol was adjusted to 230 ° C after 3 hours. The transesterification reaction was substantially terminated after 4 hours. The reaction mixture was transferred to a polycondensation tank, and after adding orthophosphoric acid, cerium oxide was added to carry out a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 280 ° C to 280 ° C. Further, the pressure was gradually reduced by normal pressure to give a final value of 0.3 mmHg. After the start of the reaction, the stirring power of the reaction tank changes, When the ultimate viscosity is equivalent to 0.63, the reaction is stopped, and the polymer is discharged under nitrogen pressure to obtain a polyester (III) having an ultimate viscosity of 0.63.

[Method of Manufacturing Polyester (IV)]

In the production method of the polyester (I), a polyester (IV) was obtained in the same manner as in the case of adding alumina particles dispersed in ethylene glycol with an average particle diameter of 0.3 μm as a particle content of 1.5% by weight of the polyester. The obtained polyester (IV) had an ultimate viscosity of 0.59 and an oligomer (ester cyclic trimer) content of 0.87% by weight.

[Method of Manufacturing Polyester (V)]

Polyester (V) was obtained except that the average particle diameter of the alumina particles was 0.04 μm and the polyester (IV) was produced. The obtained polyester (V) had an ultimate viscosity of 0.59 and an oligomer (ester cyclic trimer) content of 0.87% by weight.

[Method of Manufacturing Polyester (VI)]

Polyester (VI) was obtained except that the average particle diameter of the alumina particles was 0.8 μm and the polyester (IV) was produced. The obtained polyester (VI) had an ultimate viscosity of 0.59 and an oligomer (ester cyclic trimer) content of 0.87% by weight.

[Method for Producing Polyester (VII)]

100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol In order to start the raw material, 0.09 part by weight of magnesium acetate tetrahydrate as a catalyst was added and placed in a reactor, and the reaction temperature was 150 ° C, and the reaction temperature was gradually raised while distilling off methanol, and it was made to be 3 hours later. 230 ° C. The transesterification reaction was substantially stopped after 4 hours. After 0.04 part of ethyl acid phosphate was added to the reaction mixture, 0.04 part of antimony trioxide was added to carry out a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 280 ° C to 280 ° C. Moreover, the pressure is gradually lowered by the normal pressure to make the final 0.3 mmHg. After the start of the reaction, the stirring power of the reaction vessel was changed, and the reaction was stopped when the ultimate viscosity was equivalent to 0.63, and the polymer was discharged under nitrogen pressure. The resulting polyester (VII) had an ultimate viscosity of 0.63.

Example 1:

The mixed raw materials obtained by mixing the above polyesters (II), (III), and (IV) in a ratio of 89.5%, 10%, and 0.5%, respectively, are used as raw materials of the layer a, and 100% of the raw materials of the polyester (I) are used as b. The raw materials of the layers are supplied to two extruders, each of which is melted at 285 ° C, and the a layer is the outermost layer (surface layer), and the b layer is the two layers of the intermediate layer (aba), and is cooled to 40 ° C. The casting drum was co-extruded under the condition that the thickness of the laminated polyester film was a:b:a=2:19:2, and the film was cooled and solidified to obtain an unoriented sheet. Next, by using a roll peripheral speed difference to extend the longitudinal direction by 3.4 times at a film temperature of 85 ° C, a coating liquid composed of a coating agent composition shown in Table 2 below was applied to both sides of the film (relative to the film traveling direction). It is the A surface, the lower side is the B surface), and the coating amount after drying on one surface is 0.012 g/m ² , and then it is introduced into a tenter, and it is extended by the 4.5 degree of the horizontal direction by 120 degreeC, and heat-processing after 230 degreeC. The film was flanked in the transverse direction, and the film was taken up by a roll to obtain a double-coated film having a coating layer having a thickness of 23 μm. Further, the compounds constituting the coating liquid shown in Table 2 are as follows, and the numerical unit in Table 2 is % by weight. Moreover, the fine adjustment of the STD can be finely adjusted by the film width after the lateral relaxation.

(Compound example)

. Polymer containing a quaternary ammonium salt (A1):

2-hydroxy 3-methacryloxypropyltrimethylammonium salt polymer

Counter ion: Methanesulfonate Number average molecular weight: 30000

. Polyethylene glycol-containing acrylate polymer (B1):

Monoacrylate polymer containing polyethylene glycol number average molecular weight: 20000

. Polyethylene glycol-containing acrylate polymer (B2):

Octyloxy polyethylene glycol-polypropylene glycol monoacrylate polymer number average molecular weight: 32000

. Crosslinking agent (C): Melamine crosslinker (made by DIC: Bekamin "MAS")

. Particle (D): Alumina surface modified colloidal ceria (average particle size: 50 nm)

. Adhesive (E): polyvinyl alcohol (degree of alkalinity 88% by mole, degree of polymerization 500)

Next, a copper oxide layer having a thickness of 20 nm is laminated on the surface of the double-coated layer of the obtained double-coated film by a sputtering method, and then patterned. The photoresist is applied onto the copper oxide layer, dried and hardened, and the obtained copper oxide layer is immersed in a 4% aqueous solution of ferric chloride for etching treatment to obtain a patterned double-sided metal laminate film. The properties of the obtained film are shown in Table 7 below.

Embodiments 2 to 17:

In addition to the coating liquid formed by the composition of the coating agent shown in Table 2 below in Example 1, the raw material addition, the longitudinal stretching ratio, the lateral stretching ratio, the main crystallization temperature, the thickness composition ratio, the film thickness, and the transverse direction relaxation A film was produced in the same manner as in the production method of Example 1 except that the film width was different.

Example 18

A film was produced in the same manner as in the production method of Example 1 except that the coating amount of the coating layer of Example 1 was changed.

Example 19

A film was produced in the same manner as in the production method of Example 1 except that the film was widened in the transverse stretching ratio and the transverse direction in Example 1.

Example 20

A film was produced in the same manner as in the production method of Example 8 except that the film was widened in the transverse stretching ratio and the transverse direction in Example 8.

Comparative Example 1:

Except for Example 1, each has a ratio of 89.5%, 10%, and 0.5%. A film was obtained in the same manner as in the production method of Example 1 except that the polyesters (I), (III) and (IV) were mixed as a raw material of the layer a.

Comparative Example 2~4:

A film was obtained in the same manner as in the production method of Example 1 except that the coating liquid formed of the coating agent composition shown in Table 2 below was changed in Example 1.

Comparative Example 5~7:

A film was produced in the same manner as in Example 1 except that the raw materials of the layer a in Example 1 were different.

Comparative Example 8:

The polyester (IV) in the surface layer of Example 1 was changed to polyester (VI), and the same method as in Example 1 was used to obtain a double-coated film, and the surface of the double-coated film was roughened. 18) In the evaluation of wiring breakage after patterning of the copper layer, it is difficult to pattern the 4 μm of the finest part. The characteristics of the obtained film are shown in Tables 3 to 11 below.

Comparative Example 9:

A film was produced in the same manner as in Example 1 except that the coating layer was not provided in Example 1.

Comparative Example 10:

Except for Example 1, each has a ratio of 10%, 0.5%, and 89.5%. A film was obtained in the same manner as in the production method of Example 1 except that the polyester (III), (IV), and (VII) were mixed as a raw material of the layer a.

The coating composition of the coating layer used in the above examples and comparative examples is shown in Table 2 below.

In the polyesters used in the above examples and comparative examples, the raw materials of the surface layer and the intermediate layer were added as shown in Tables 3 to 5 below.

The properties of the films obtained in the above examples and comparative examples are shown in Tables 6 to 8 below.

Industrial use possibility

The double-sided metal laminate film of the present invention is suitably used for, for example, a flexible double-sided circuit board application, and a constituent member for a touch panel (for example, a conductive film or the like).

Claims (5)

A two-sided metal laminate film characterized in that the polyester film has coating on both sides thereof with a coating liquid containing a compound containing a quaternary ammonium salt group, an acrylate polymer containing polyethylene glycol, and a crosslinking agent. Layers, each of which is laminated on the coating layer. The two-layer metal laminated film of claim 1, wherein the content of the compound containing a quaternary ammonium salt group is 20 to 70% by weight, based on the ratio of all solid components in the coating liquid for forming the coating layer, comprising polyethylene The content of the polymer of the diol is 5 to 40% by weight, and the content of the crosslinking agent is 10 to 60% by weight. A two-sided metal laminate film according to claim 1 or 2, wherein the metal layer is a patterned metal layer. The two-sided metal laminate film according to any one of claims 1 to 3, wherein the metal layer is a copper layer. The two-sided metal laminate film according to any one of claims 1 to 4, which is in accordance with the following formula: SMD-STD|≦0.5 (in the above formula, SMD is a shrinkage ratio (%) indicating a film running direction (MD) STD indicates the shrinkage ratio (%) in the direction (TD) orthogonal to the film running direction.