JP4963628B2 - Polymer film laminate, method for producing the same, and flexible wiring board using polymer film laminate. - Google Patents

Description

  The present invention relates to a polymer film laminate, a method for producing the same, and a flexible wiring board using the polymer film laminate.

  A flexible wiring board (hereinafter abbreviated as “FPC”) is flexible and has a high degree of spatial freedom, so that it can be mounted with high density, and therefore has a wiring, cable, or connector function. It is used for various electronic devices as composite parts. In recent years, electronic devices have been reduced in size and weight, and in order to cope with this, FPCs mounted on electronic devices are also required to be reduced in size and associated with circuit miniaturization.

  The FPC is generally obtained by using a polymer film laminate in which a polymer film layer is formed on a metal foil and circuitizing the metal foil. In this case, in order to achieve circuit miniaturization, high adhesion between the metal foil and the polymer film layer is required. From this viewpoint, as the polymer film laminate, a so-called two-layer FCCL in which polymer film layers such as polyimide, polyimide benzoxazole, and polyamideimide are produced by cast film formation is often used. Recently, a liquid crystal polyester film laminate having a resin layer containing an aromatic liquid crystal polyester is suitable for FPC applications because the resin layer has low water absorption and excellent electrical insulation properties such as insulation and high frequency characteristics. (See Patent Document 1).

  Here, in the production of the polymer film laminate as described above, an operation of once forming a layer made of a precursor of the polymer film and then completing the polymer film layer by performing a heat treatment is performed. There are many. For example, in the case of the above-mentioned two-layer FCCL, a polymer film layer is formed by forming a layer made of a precursor such as polyimide, polyimide benzoxazole, or polyamideimide, and then causing an imide ring-closing reaction by heat treatment (Patent Document 2). reference). Also, in the case of a liquid crystal polyester film laminate, after the liquid crystal polyester layer is once formed, heat treatment is further performed to improve the characteristics (see Patent Document 3).

  On the other hand, the polymer film laminate as described above is desirably supplied in the form of a roll from the viewpoint of ease of storage and conveyance. Therefore, as an efficient method for producing a polymer film laminate, first, a rolled body is formed in the state of a laminate having a polymer film precursor layer to form a wound body, and then the obtained wound body is heat-treated. Thus, a method for forming a polymer film layer from a precursor layer is known. However, in this case, when heat treatment is performed in a roll state, there is a possibility that adhesion between the wound laminates may occur, and therefore winding is performed while sandwiching the spacer (see Patent Document 4). .

When winding with a spacer, if the spacer is placed so that the entire surface of the precursor layer of the polymer film is covered, adhesion between the polymer film and the spacer may occur, or the surface of the spacer There arises a new problem that the shape is transferred to the polymer film. In order to avoid such inconvenience, a method has been proposed in which a spacer made of a fabric-like material is disposed only at both end portions and winding is performed. The spacer made of this fabric-like material is made of cellulose fiber, glass fiber, carbon fiber, aramid fiber, alumina fiber, polybenzoxazole fiber, metal fiber, metal wire, woven fabric, nonwoven fabric, or heat-resistant material. A porous body having a through hole has been proposed (see Patent Document 5).
JP 2005-342980 A JP-A-62-212140 JP 2006-088426 A Japanese Patent Laid-Open No. 04-084488 JP 2005-131918 A

  Although it is possible to reduce adhesion between laminates due to winding by applying a spacer as in the prior art described above, when forming a polymer film that is extremely easy to adhere, such as a liquid crystal polyester film, It is desirable to prevent almost completely from occurring. When the spacer is thin, adhesion may occur partially due to a deflection of the central region far from the spacer. Therefore, from the viewpoint of reliably preventing adhesion, it is preferable to make the spacer as thick as possible.

  However, as a result of the study by the present inventors, it has been found that when the spacer is made thick in order to reliably prevent adhesion, the following problems are likely to occur based on the increase in weight. That is, since the high-weight spacer has a large heat capacity, when the polymer film precursor is subjected to heat treatment, it consumes much heat applied to the wound body, and as a result, is necessary for the heat treatment. It has been found that increasing the treatment time and the amount of heat causes a decrease in the productivity of the polymer film laminate.

  That is, when the heat capacity of the spacer is large, due to the heat consumption of the spacer, the inner peripheral part tends to follow the heat treatment temperature significantly slower than the outer peripheral part of the wound body. In this case, it is necessary to perform heating for a long time in accordance with the inner peripheral portion that is difficult to receive heat history, and excessive energy and cost are required for the heat treatment. In addition, due to the difference in thermal history, there is a difference in the characteristics of the polymer film obtained between the outer peripheral part and the inner peripheral part of the wound body, or the outer peripheral part is heated more than necessary, and this part of the polymer film deteriorates. It may occur.

  Furthermore, if the spacer is heavy, the operability is deteriorated, and the weight of the winding body in one production lot is excessively increased, making it difficult to produce many polymer film laminates at once. There was also. For these reasons, the spacer is currently required to be as light as possible within a range where a sufficient function can be obtained.

  Therefore, the present invention has been made in view of such circumstances, and a polymer film laminate is obtained by winding up a laminate in which a polymer film precursor layer is formed on a metal foil and heat-treating the laminate. It is an object of the present invention to provide a method for producing a polymer film laminate capable of producing a homogeneous polymer film laminate with high productivity while sufficiently suppressing adhesion in winding of the laminate. And Another object of the present invention is to provide a polymer film laminate obtained by such a production method, and a flexible wiring board using the polymer film laminate.

In order to achieve the above-mentioned object, the method for producing a polymer film laminate of the present invention winds up a laminate in which a precursor layer made of a precursor of a polymer film is formed on a metal foil to obtain a wound body The first step and a second step of obtaining a polymer film laminate in which a polymer film is formed on a metal foil by heat-treating the wound body, and the laminates wound up in the first step Spacers are arranged along the sides located at both ends in the direction intersecting the winding direction of the laminated body so as to be sandwiched between them, and the laminated body is wound up and protrudes to at least one surface side as a spacer. The apparent thickness represented by the distance between the surface connecting the top of the convex part and the surface where the convex part is not formed is composed of a wire mesh in which the convex part is formed so as to be repeatedly formed on the entire surface. 0.5-3m There use is what is, the polymer film is characterized by consisting of a liquid crystal polyester.

The method for producing a polymer film laminate of the present invention includes a first step of winding a laminate in which a precursor layer made of a precursor of a polymer film is formed on a metal foil to obtain a wound body, A second step of obtaining a polymer film laminate in which a polymer film is formed on a metal foil by heat-treating the wound body, and sandwiched between the laminates to be wound in the first step As described above, the spacers were arranged along the sides located at both ends in the direction intersecting with the winding direction of the laminated body, and the laminated body was wound up and formed as a spacer so as to protrude alternately on the opposite side. The distance between the surface connecting the top of the first protrusion and the surface connecting the top of the second protrusion, which is composed of a wire mesh in which the first protrusion and the second protrusion are repeatedly provided on substantially the entire surface. The apparent thickness represented by 0.5-3mm There use a shall, polymer film is characterized by consisting of a liquid crystal polyester.

  In the manufacturing method of the present invention, spacers are sandwiched between the laminated bodies adjacent in the circumferential direction by winding at both ends of the wound body. At this time, since the metal mesh constituting the spacer has a concavo-convex shape with protruding protrusions, the adjacent laminates are not formed on the top of the protrusions and the non-forming surface of the protrusions, or the first protrusions. Supported by the top of each of the portions and the top of the second convex portion. Therefore, in the present invention, at the time of winding, it is expressed by the distance between the top part of the convex part and the non-formed surface of the convex part, or between the top parts of the first convex part and the second convex part. Adjacent laminates are separated from each other by the apparent thickness of the spacer. And in this invention, since this apparent thickness is 0.5-3 mm and sufficiently large, the adhesion | attachment of the laminated bodies by winding can fully be prevented.

  In addition, since the apparent thickness of the spacer is increased by the formation of the convex portion, the wire mesh itself constituting the spacer may be thin, so that it is significantly larger than a spacer having an actually equivalent thickness. Weight reduction is possible. Therefore, according to the present invention, it is possible to reduce the influence of the heat capacity of the spacer and obtain good productivity as compared with the case of using the thick and heavy spacer as described above. Furthermore, since the heat capacity of the spacer is small as described above, it is difficult to cause a difference in the degree of heat treatment between the outer peripheral portion and the inner peripheral portion of the wound body, thereby making it possible to obtain a homogeneous polymer film laminate. It becomes.

  Further, conventionally, when a thick spacer is used, the elasticity thereof is large, so it often happens to repel at the time of winding, but the spacer in the present invention has such a repulsion because the thickness of the wire mesh itself is small. Not likely to occur. Therefore, according to the manufacturing method of the present invention, good workability can be obtained.

  In the method for producing a polymer film laminate of the present invention, it is more preferable to use a spacer having an apparent thickness of 1 to 2 mm. Thereby, it becomes possible to more reliably prevent adhesion between the laminates during winding.

  The present invention also provides a polymer film laminate obtained by the production method of the present invention. Furthermore, this invention provides the flexible wiring board using the polymer film laminated body of this invention. Since these polymer film laminates and flexible wiring boards are obtained through the production method of the present invention, the polymer film is hardly affected by adhesion during production, and has a good shape and A polymer film having characteristics is provided.

  According to the present invention, in a production method of winding a laminate in which a polymer film precursor layer is formed on a metal foil and obtaining a polymer film laminate by heat-treating the laminate, It is possible to provide a method for producing a polymer film laminate that can produce a polymer film laminate having uniform quality in a lot of wound bodies with high productivity while sufficiently suppressing adhesion. Moreover, it becomes possible to provide the polymer film laminated body and flexible wiring board which are obtained through such a manufacturing method and are provided with the polymer film which has a favorable shape and characteristic.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as necessary.
[Polymer film laminate]

  First, the structure of the polymer film laminated body obtained by the manufacturing method which concerns on suitable embodiment of this invention is demonstrated. FIG. 1 is a diagram schematically showing a cross-sectional configuration of a polymer film laminate according to a preferred embodiment. As illustrated, the polymer film laminate 1 has a configuration in which a polymer film 4 is laminated on a metal foil 2.

  The metal foil 1 is composed of, for example, a foil, a thin film, a sheet-like film, or the like made of a metal such as gold, silver, copper, aluminum, or nickel. When the polymer film laminate 1 is used for FPC, the metal foil 1 is preferably a copper foil from the viewpoint of conductivity and cost. The metal foil 1 preferably has a width in the short direction of about 150 to 1500 mm and a width in the longitudinal direction of about 1 to 6000 m, but is appropriately selected depending on the size required for the polymer film laminate 1. Can be changed.

  The polymer film 4 is composed of a polymer compound capable of forming a film, and is preferably composed of a resin material such as polyimide, polyamideimide, polyimide benzoxazole, or liquid crystal polyester. Among these, when applied to FPC, liquid crystal polyester is preferable because of its low water absorption and excellent electrical insulation.

  The thickness of the metal foil 2 in the polymer film laminate 1 is preferably 3 to 70 μm, and more preferably 9 to 35 μm. The thickness of the polymer film 4 is preferably about 1 to 500 μm from the viewpoint of improving the film formability and mechanical properties, and from 1 to 200 μm from the viewpoint of further improving the handleability. More preferably.

  Here, the liquid crystal polyester which is a suitable material for forming the polymer film 4 will be described more specifically.

  As the liquid crystal polyester, an aromatic liquid crystal polyester having an aromatic ring in the repeating unit is preferable, and an aromatic liquid crystal polyester soluble in a solvent is more preferable. Examples of such aromatic liquid crystal polyesters include aromatic liquid crystal polyesters that are soluble in halogenated phenols and aprotic solvents disclosed in Japanese Patent Application Laid-Open Nos. 2004-269874 and 2005-342980. . Among these, an aromatic liquid crystal polyester that is easily applied to the method for producing the polymer film laminate 1 described later and is soluble in an aprotic solvent is preferable.

  Aromatic liquid crystalline polyesters soluble in aprotic solvents include structural units derived from aromatic hydroxycarboxylic acids, aromatic diols, aromatic diamines, aromatic amines having hydroxyl groups, aromatic dicarboxylic acids, etc. as raw material compounds, respectively. The thing which has is mentioned.

In particular, from the viewpoint of developing good liquid crystallinity, the aromatic liquid crystal polyester has a structural unit represented by the following formula (1) derived from an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic diamine, and a hydroxyl group. A structural unit represented by the following formula (2) derived from at least one compound selected from the group consisting of aromatic amines, and a formula (3) derived from an aromatic dicarboxylic acid Those having a combination of structural units are preferred. In addition, aromatic liquid crystal polyester may have 2 or more types of structural units represented by said (1)-(3), respectively.
(1) —O—Ar ¹ —CO—
(2) ^-X-Ar 2 -Y-
(3) —CO—Ar ³ —CO—

In the above formula, Ar ¹ is at least one group selected from the group consisting of 1,4-phenylene, 2,6-naphthylene and 4,4′-biphenylene, Ar ² is 1,4-phenylene, It is at least one group selected from the group consisting of 1,3-phenylene and 4,4′-biphenylene. X and Y are groups represented by —O— or —NH—, respectively. Ar ³ is at least one group selected from the group consisting of 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, and a group represented by the following formula (4).
(4) —Ar ⁴ —Z—Ar ⁵ —

In the formula (4), Ar ⁴ and Ar ⁵ are each independently at least one group selected from the group consisting of 1,4-phenylene, 2,6-naphthylene and 4,4′-biphenylene. . Furthermore, Z is at least one group selected from the group consisting of groups represented by —O—, —SO ₂ — and —CO—.

  Here, examples of the structural unit (1) include structural units derived from p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'-biphenylcarboxylic acid, and the like. Of these, structural units derived from 2-hydroxy-6-naphthoic acid are preferred. Examples of the structural unit of the above formula (2) include 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, and 4-hydroxy. And structural units derived from -4′-biphenyl alcohol and the like. Especially, the structural unit derived from 4-aminophenol is preferable from a reactive viewpoint at the time of aromatic liquid-crystal polyester manufacture.

  Examples of the structural unit of the above formula (3) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, benzophenone— Examples include structural units derived from 4,4′-dicarboxylic acid and the like. Among these, from the viewpoint of improving the solubility in a solvent, a structural unit derived from isophthalic acid or a structural unit derived from diphenyl ether-4,4′-dicarboxylic acid is preferable.

  The aromatic liquid crystal polyester containing the structural units of the above formulas (1) to (3) preferably has these structural units in the proportions shown below. That is, the ratio of the structural unit of the formula (1) is preferably 30 to 80 mol%, more preferably 35 to 65 mol%, and further preferably 40 to 55 mol% with respect to all the structural units. . When the structural unit of the formula (1) is contained at such a ratio, the solubility of the aromatic liquid crystal polyester in the solvent becomes good, and it becomes easy to apply to a solution casting method suitable for the production method described later. In addition, the liquid crystallinity is maintained well.

  Moreover, the ratio of the structural unit of the formula (2) is preferably 10 to 35 mol%, more preferably 17.5 to 32.5 mol%, based on all structural units, and 22.5 to 30.30. More preferably, it is 0 mol%. When such a ratio is satisfied, the solubility of the aromatic liquid crystal polyester in the solvent becomes good and excellent liquid crystal properties can be obtained.

  Furthermore, the ratio of the structural unit of the formula (3) is preferably 35 to 10 mol%, more preferably 17.5 to 32.5 mol% with respect to all the structural units, and 22.5 to 30.30. More preferably, it is 0 mol%.

  Furthermore, the content ratio of the structural unit of the formula (2) and the content ratio of the structural unit of the formula (3) are [the content ratio of the structural unit of the formula (2) / the content ratio of the structural unit of the formula (3). ] (The unit of the content ratio of each structural unit is mol%), it is preferable to satisfy 0.85 to 1.25, particularly preferably close to 1. That is, it is particularly preferable that the content ratio of the structural unit of the formula (2) and the content ratio of the structural unit of the formula (3) are substantially equal. If such conditions are satisfied, the degree of polymerization of the aromatic liquid crystal polyester tends to be good.

  The aromatic liquid crystal polyester is obtained by polymerizing a compound (monomer) derived from each structural unit as described above by a known method described in JP-A No. 2002-220444, JP-A No. 2002-146003, or the like. Can be manufactured by. In order to obtain an aromatic liquid crystal polyester having the structural units of the above formulas (1) to (3), for example, first, a phenolic hydroxyl group in an aromatic hydroxycarboxylic acid that is a raw material compound of the structural unit of the formula (1), and The phenolic hydroxyl group or amino group in the aromatic diol, aromatic diamine or aromatic amine having a hydroxyl group, which is a raw material compound of the structural unit of the formula (2), is acylated by reacting with an excess amount of fatty acid anhydride. Gives rise to chemicals. Next, an ester exchange / amide exchange (polycondensation) reaction is caused between the obtained acylated product and an aromatic dicarboxylic acid which is a raw material compound of the structural unit of the formula (3) to carry out an aromatic reaction. Group liquid crystal polyester can be obtained.

  In the acylation reaction, the amount of fatty acid anhydride added is preferably 1.0 to 1.2 times equivalent to the total of the phenolic hydroxyl group and amino group of the raw material compound. It is more preferable to set it to -1.1 times equivalent. When the amount of the fatty acid anhydride added is within this range, it is difficult to cause sublimation of the acylated product or its raw material compound in the subsequent transesterification / amide exchange reaction, and the inconvenience that the reaction system is blocked can be avoided. . As a result, the resulting aromatic liquid crystal polyester tends to be significantly less colored. The acylation reaction is preferably performed at 130 to 180 ° C. for 5 minutes to 10 hours, more preferably 140 to 160 ° C. for 10 minutes to 3 hours.

  Examples of the fatty acid anhydride used in the acylation reaction include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, anhydrous Trichloroacetic acid, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β-bromopropionic anhydride, etc. These may be used in combination of two or more. From the viewpoint of handleability and cost, acetic anhydride, propionic anhydride, butyric anhydride or isobutyric anhydride is preferable, and acetic anhydride is more preferable.

  In the transesterification / amide exchange reaction subsequent to the acylation reaction, the total of acyl groups in the acylated product is preferably 0.8 to 1.2 times equivalent to the total of carboxyl groups in the aromatic dicarboxylic acid. The transesterification / amide exchange reaction is preferably caused to occur at a rate of 0.1 to 50 ° C./min up to 400 ° C., for example, and at a rate of 0.3 to 5 ° C./min up to 350 ° C. More preferably, it is generated while raising the temperature. During the reaction, it is preferable to remove the by-produced fatty acid and the unreacted fatty acid anhydride from the reaction system by evaporating or the like in order to move the equilibrium and favor the production of the aromatic liquid crystalline polyester.

  The acylation reaction and transesterification / amide exchange reaction in the production of the aromatic liquid crystal polyester as described above may be performed in the presence of a catalyst. If it carries out like this, reaction can be performed efficiently on mild conditions and manufacture of aromatic liquid crystal polyester can be performed more favorably. As the catalyst, those used as a catalyst for polyester polymerization can be applied, and among them, metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. And organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole are preferred. In particular, heterocyclic compounds containing two or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are preferred. When these catalysts are used, the catalysts are added before the reaction. For example, the catalyst used in the acylation reaction may be used as it is in the transesterification / amide exchange reaction without being removed after the reaction.

  The polycondensation by transesterification / amide exchange reaction can be performed by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination. The solid phase polymerization can be carried out by extracting a polymer from the melt polymerization step, pulverizing it into powder or flakes, and then applying a known solid phase polymerization method. For example, the method of heat-processing in a solid-state state at 150-350 degreeC under inert atmosphere, such as nitrogen, for 1 to 30 hours is mentioned. The solid phase polymerization may be performed with stirring, or may be performed in a state of standing without stirring. In addition, melt polymerization and solid phase polymerization can also be performed in the same reaction tank by providing an appropriate stirring mechanism. After the solid state polymerization, the obtained aromatic liquid crystal polyester may be pelletized by a known method and then molded.

The aromatic liquid crystal polyester can be produced using, for example, a batch apparatus, a continuous apparatus or the like. And the aromatic liquid crystal polyester soluble in an aprotic solvent can be obtained by the manufacturing method as described above.
[Method for producing polymer film laminate]

  Next, the manufacturing method of the polymer film laminated body which concerns on suitable embodiment is demonstrated. A method for producing a polymer film laminate according to a preferred embodiment includes a first step of winding a laminate in which a precursor layer made of a precursor of a polymer film is formed on a metal foil to obtain a wound body, Heat-treating the wound body to obtain a polymer film laminate in which a polymer film is formed on the metal foil.

  FIG. 2 is a diagram schematically showing a step of winding the laminate in the first step. As shown in the drawing, in the first step, continuous along the sides located at both ends in the direction intersecting the winding direction of the laminated body 10 so as to be sandwiched between the laminated bodies 10 to be wound. Thus, the spacer 30 is arranged and the laminated body 10 is wound up to obtain the wound body 100. In FIG. 2, the spacer 30 is schematically shown, and the detailed form of the spacer 30 will be described later.

  In such a 1st process, the laminated body 10 is prepared first. The laminate 10 includes a metal foil 2 and a precursor layer 14 made of a polymer film precursor formed on the metal foil 2. The metal foil 2 is the same as the metal foil 2 in the polymer film laminate 1 described above.

  On the other hand, the precursor layer 14 formed on the metal foil 2 is a layer that can form the polymer film 4 described above by heat treatment. For example, it is comprised from the layer containing the precursor compound before producing the imide ring closure in manufacture of a polyimide, polyamideimide, polyimide benzoxazole, etc., and the layer containing aromatic liquid crystal polyester before heat processing. In addition, the precursor layer 14 is not necessarily limited to the layer comprised from the precursor compound of the polymer film 4, For example, the layer which becomes the polymer film 4 only by removing a solvent by heat processing is also the precursor layer 14. include.

  In the laminate 10 having the above-described configuration, for example, a method of laminating the precursor layer 14 and the metal foil 2 manufactured in advance by lamination, or a solution composition for forming the precursor layer 14 on the metal foil 2 is used. It can be obtained by a cast solution casting method. In particular, the latter solution casting method is preferable. According to the solution casting method, in addition to easy operation, the adhesion between the metal foil 2 and the polymer film 4 can be improved. In the solution casting method, for example, after casting the solution composition on the metal foil 2, the solvent in the solution composition is removed to form the precursor layer 14, thereby obtaining the laminate 10.

  Here, the solution casting method which is a suitable manufacturing method of the precursor layer 14 is demonstrated in detail. Examples of the solution composition used in the solution casting method include a solution containing a polyamic acid compound that is a precursor of the polymer film 4 made of polyimide, polyamideimide, or polyimidebenzoxazole. Such a solution composition can be obtained, for example, by dissolving raw material monomers diamine and acid dianhydride in N-methyl-2-pyrrolidone (NMP) or the like and then reacting the raw material monomers with each other.

  On the other hand, when forming the polymer film 4 which consists of liquid crystal polyester, as a solution composition, what was obtained by melt | dissolving the liquid crystal polyester mentioned above in the aprotic solvent is mentioned. As this solution composition, what dissolved 0.01-100 weight part of liquid crystalline polyester with respect to 100 weight part of aprotic solvents is mentioned. Since such a solution composition has an appropriate solution viscosity, it can be applied uniformly when applied to the solution casting method.

  Especially as a solution composition containing liquid crystal polyester, what contains 1-50 weight part of liquid crystal polyester with respect to 100 weight part of aprotic solvents is preferable, and what contains 2-40 weight part is more preferable. According to such a solution composition, not only better workability can be obtained, but also the cost can be reduced.

  Examples of the aprotic solvent include halogen solvents such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, diethyl ether, tetrahydrofuran, Ether solvents such as 1,4-dioxane, ketone solvents such as acetone and cyclohexanone, ester solvents such as ethyl acetate, lactone solvents such as γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, triethylamine, Amine solvents such as pyridine, nitrile solvents such as acetonitrile and succinonitrile, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and N-methylpyrrolidone, nitrometa Nitro-based solvents such as nitrobenzene, dimethyl sulfoxide, sulfide-based solvents such as sulfolane, hexamethylphosphoramide, and phosphoric acid-based solvent such as tri -n- butyl phosphate and the like.

  Among these, as the aprotic solvent, a solvent containing no halogen atom is preferable because it can reduce the burden on the environment, and a solvent having a dipole moment of 3 to 5 is a liquid crystal polyester (particularly an aromatic liquid crystal polyester). Is more preferable because it can be dissolved well. Specific examples of such aprotic solvents include amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and N-methylpyrrolidone, or γ-butyrolactone. Lactone solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide or N-methylpyrrolidone are particularly preferable. The solution composition may contain a solvent other than the aprotic solvent to the extent that the production of the polymer film laminate is not inhibited.

  The solution composition containing polyimide or aromatic liquid crystal polyester as described above may contain fine foreign matters that are by-produced or mixed at the time of production. Such foreign matters are filtered by a filter or the like. It may be removed. In addition, the solution composition may further contain components other than those described above as necessary in order to obtain desired characteristics of the polymer film 4. Examples of other components include fillers and thermoplastic resins.

  Examples of the filler include organic fillers such as epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder, and styrene resin powder, silica, alumina, titanium oxide, zirconia, kaolin, calcium carbonate, calcium phosphate, and boron. Examples thereof include inorganic fillers such as aluminum oxide, potassium titanate, magnesium sulfate, zinc oxide, silicon carbide, silicon nitride, glass fiber, and alumina fiber.

  In addition, as thermoplastic resins, elastomers such as polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and modified products thereof, polyether imide, and a copolymer of glycidyl methacrylate and polyethylene Etc.

  In addition, the solution composition may further contain additives such as a coupling agent, an anti-settling agent, an ultraviolet absorber, and a heat stabilizer.

  In the production of the laminate 10 by the solution casting method, the above-described solution composition is cast and applied onto the metal foil 2, and then the solvent in the solution composition is removed to remove the solvent from the polymer film precursor. A precursor layer 14 is formed. Examples of casting / coating methods include roller coating, gravure coating, knife coating, blade coating, rod coating, dip coating, spray coating, curtain coating, slot coating, and screen printing. Etc. Among these, the knife coat method or the slot coat method is preferable because control is easy and the film thickness can be made uniform with high accuracy.

  The method for removing the solvent after coating is not particularly limited, but it is preferably performed by evaporating the solvent, for example. Examples of the method for evaporating the solvent include methods such as heating, decompression, and ventilation. Of these, evaporation by heating is preferable because of good production efficiency and good handleability, and evaporation by heating while ventilating is more preferable.

  As a method for removing the solvent, specifically, the laminate in a state where the solution composition is cast applied on the metal foil 2 is guided to a winding process as described later. There is a method in which the solvent is removed by passing through a heating furnace while running. Although the temperature and time required for solvent removal are not particularly limited, for example, the temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower. If the temperature is too high, defects may occur on the coating surface. On the other hand, if the temperature is too low, the time for removing the solvent becomes long, and the productivity may be lowered. Therefore, the solvent removal is preferably performed at least at 60 ° C. or higher.

  When the polymer film 4 is formed of an aromatic liquid crystal polyester, it is preferable to remove the solvent so that the precursor layer 14 has a remaining solvent amount of 18% by weight or less. If the amount of the remaining solvent is 18% by weight or less, preferably 15% by weight or less, the precursor layer 14 becomes almost dry, and adhesion occurs even if the laminate 10 comes into contact before the heat treatment described later. It becomes difficult to occur, and the workability during the winding process tends to be improved.

  Hereinafter, the first step will be described with reference to FIG. 2 again. In a 1st process, the laminated body 10 obtained as mentioned above is wound up, and the wound body 100 is obtained. At the time of winding, spacers 30 are continuously arranged on the precursor layer 14 of the laminated body 10 along both sides in the longitudinal direction of the laminated body 10, and the spacers 30 are also taken up together with the laminated body 10. . As a result, the spacers 30 are sandwiched between the laminated bodies 10 that are stacked in the circumferential direction by winding at both ends of the wound body 100, and as a result, the laminated bodies 10 that are adjacent in the circumferential direction are in contact with each other. Not to be.

  In the first step, the laminate 10 may be wound up as it is, and then wound together with the spacers 30 using this. In this case, since the precursor layer 14 after drying does not cause adhesion unless it is heat-treated, adhesion at the initial winding hardly causes a problem.

  The spacer 30 is composed of a wire mesh and preferably has a long shape so as to extend along both sides in the direction in which the laminate 10 is wound. The spacer 30 has a predetermined uneven shape in the surface direction. In the first step, the spacer 30 is arranged so that the surface direction thereof is along the surface direction of the stacked body 10.

  Here, FIG. 3 is a diagram partially showing a planar shape of the spacer 30 of the preferred embodiment. FIG. 4 is a diagram schematically showing a cross-sectional structure taken along line IV-IV of the spacer 30 shown in FIG. As shown in FIGS. 3 and 4, the spacer 30 is formed with a protrusion 32 (first protrusion) formed so as to protrude toward one side of the spacer 30 and a protrusion formed on the opposite side of the protrusion 32. The protrusions 34 (second protrusions) are alternately and repeatedly provided. Although not shown, the spacer 30 also has a cross section in a direction intersecting with the cross section shown in FIG. 4 in which convex portions 32 and concave portions 34 are alternately and repeatedly provided in the same manner as in FIG.

  The convex portion 32 and the convex portion 34 are formed on the substantially entire surface of the spacer 30 by being continuously formed adjacent to each other. Each of the convex portions 32 and the convex portions 34 has a substantially quadrangular pyramid shape having a trapezoidal cross section. In addition, the shape of the convex parts 32 and 34 is not restricted to the pyramid shape represented by such a quadrangular pyramid shape, A cone, a truncated cone, a hemispherical surface, a pyramid etc. may be sufficient.

  In this spacer 30, the apparent thickness of the spacer 30 represented by the distance between the surface connecting the tops of the protrusions 32 and the surface connecting the tops of the protrusions 34 is preferably 0.5 to 3 mm. 1 to 2 mm is more preferable. In the spacer 30 of this embodiment, as shown in FIG. 4, for example, the distance h between the top surfaces of the convex portions 32 and 34 having a quadrangular pyramid shape corresponds to the apparent thickness of the spacer 30.

  In a 1st process, the spacer 30 is arrange | positioned between the laminated bodies adjacent by winding at the edge part of a winding body. At this time, the adjacent stacked bodies are respectively supported by the convex portions 32 and the convex portions 34, so that they are separated by the apparent thickness of the spacer 30. Therefore, since the spacer 30 has the above apparent thickness, the adjacent laminated bodies are sufficiently separated from each other by winding, and as a result, it is possible to prevent adhesion of the laminated bodies due to winding. Become.

  The size of the convex portion 32 or the convex portion 34 in the spacer 30 in the width direction is preferably 1 to 20 times the apparent thickness, and more preferably 2 to 10 times. In addition, the magnitude | size of this width direction may differ with directions. In the case of the present embodiment, for example, the size in the width direction of the convex portion 32 is represented by a distance p between intersections of the convex portion 32 with the convex portion 34 in the cross section of the spacer 30 as shown in FIG.

  As the wire mesh constituting the spacer 30, for example, those formed by various weaving methods such as plain weave, twill weave, plain tatami mat, twill mat weave, stranded wire weave, and the like can be applied. Of these, plain woven wire mesh and twill woven wire mesh are preferable. The mesh and wire diameter of the wire mesh can be selected optimally depending on the apparent thickness of the desired spacer, but is preferably 25 to 400 mesh from the viewpoint of suitably obtaining the strength of the convex portions 32 and 34 and the weight of the spacer. It is more preferable that it is -200 mesh.

  A spacer formed of a wire mesh having a mesh that is too fine tends to collapse part of the protrusions 32 and 34 when the laminate 10 is wound, and can sufficiently prevent contact between the laminates 10. There is a risk of disappearing. On the other hand, when a wire mesh having a mesh that is too coarse is used, the weight of the spacer 30 may increase, or the winding workability of the spacer 30 may decrease.

  As the wire mesh applied to the spacer 30, for example, one made of stainless steel such as SUS304, SUS304L, SUS316, or SUS316L is preferable because of its excellent heat resistance and chemical resistance. Further, the thickness of the wire mesh constituting the spacer 30 is preferably 50 to 600 μm, and more preferably 100 to 400 μm.

  The method for forming the spacer 30 having such a shape is not particularly limited. For example, a shape plate or a roller having a concavo-convex molding surface capable of transferring a target convex shape is used, and the molding surface is planar. There is a method of continuously pressing the metal mesh and transferring these uneven patterns to the metal mesh. Such transfer can be performed by, for example, progressive pressing, embossing, or the like. More specifically, in accordance with the method described in Japanese Patent Application Laid-Open No. 2003-33725, it is possible to manufacture a wire mesh having convex portions.

  In the first step, the laminate 10 can be wound so that one end in the winding direction is fixed to a predetermined core and the laminate 10 is wound around the core. At this time, the spacers 30 are sequentially fed out so as to be disposed on both end regions in the longitudinal direction of the laminated body 10, whereby the spacers 30 are also wound up together with the laminated body 10.

  Although it is preferable to adjust suitably the speed | rate at the time of winding up the laminated body 10 with the shape of the wound body 100, and the dimension of the laminated body 10, it can be set as the range of 0.1-100 m / min, for example. Also, take-up can be done by forcibly rotating the take-up part, or the take-up part can be freely rotated, and an appropriate guide roll is placed halfway up to the take-up part. The method of sending out the laminated body 10 to a winding-up part by rotating is mentioned. In winding, a tension that does not cause breakage may be applied so that the laminate 10 does not bend greatly.

  As the winding core used for winding, those having an outer diameter of preferably 30 to 500 mmφ, more preferably 40 to 300 mmφ, still more preferably 50 to 200 mmφ, and particularly preferably 60 to 158 mmφ can be applied. Moreover, when the outer diameter of the wound body 100 before heat treatment that combines the core and the laminate 10 is 60 to 158 mmφ as the core, preferably 60 to 500 mmφ, and more preferably 90 to 90 mm. 400 mmφ. The material of the core is preferably one that has chemical resistance in addition to heat resistance that can withstand heat treatment conditions and that can withstand the weight of the laminate 10 and the spacer 30 during heat treatment. Examples of such a material for the core include iron, copper, aluminum, titanium, nickel, and alloys thereof. In particular, the core is preferably made of a magnesium-based aluminum alloy such as A5052, A5056, or A5083, or stainless steel such as SUS304, SUS304L, SUS316, or SUS316L.

  In winding, the spacers 30 are respectively arranged along both end portions of the laminate 10 as described above. The width of the spacer 30 in the short direction is smaller than the width of the laminate 10 in the short direction. The total amount is preferably 10 to 20%, and more preferably 5 to 10%. In general, the region where the spacer 30 is arranged cannot be used as the polymer film laminate 1 because the surface shape of the spacer 30 is usually transferred to the polymer film 4. On the other hand, by making the width of the spacer 30 in the above-described range, it is possible to sufficiently prevent contact between the laminates 10 by winding while minimizing the area that cannot be used as the polymer film laminate 1. .

  After obtaining the wound body 100 by the first step described above, the wound body 100 is subjected to heat treatment in the second step. By this heat treatment, the polymer film 4 is formed from the precursor layer 14, and the polymer film laminate 1 in which the polymer film 4 is laminated on the metal foil 2 is obtained.

  The heat treatment is preferably performed under conditions such that the polymer film 4 is appropriately formed from the precursor layer 14. For example, when forming a polymer film 4 such as polyimide, the condition is such that an imide ring-closing reaction of a polyamic acid that is a precursor compound thereof, and when forming a polymer film 4 made of a polymer liquid crystal polyester, The conditions are such that the polymer film 4 having sufficient characteristics such as tensile strength and peel strength is formed from the precursor layer 14.

  Specifically, the treatment temperature during the heat treatment is preferably in the range of 200 ° C to 350 ° C. The lower limit of this temperature range is more preferably 250 ° C, and even more preferably 280 ° C. On the other hand, the upper limit of the treatment temperature is more preferably 340 ° C, and further preferably 330 ° C. The heat treatment time is preferably in the range of 10 minutes to 15 hours. The lower limit of this treatment time is more preferably 20 minutes and even more preferably 40 minutes. On the other hand, the upper limit of the treatment time is more preferably 12 hours, and even more preferably 10 hours. In the heat treatment, from the viewpoint of preventing deterioration of the metal foil 2 due to oxidation, the heat treatment environment may be replaced with an inert gas such as nitrogen, argon, neon, or a vacuum.

  As a heat treatment method, for example, a method in which the wound body 100 is placed in a heating and ventilation type heating furnace and heated by hot air is suitable. In this case, the processing temperature can be controlled by setting the hot air to a predetermined temperature. And according to this invention, since the inner peripheral part and outer peripheral part of the winding body 100 can follow hot air temperature (atmosphere temperature) substantially similarly, the heat history of the inner peripheral part and outer peripheral part in the winding body 100 is demonstrated. Can be made uniform, and a homogeneous polymer film laminate can be obtained for each lot of the wound body.

  After the heat treatment in the second step, the winding body 100 is cooled, the polymer film laminate 1 is fed out from the winding body 100, and cutting, removal of the spacers 30 and the like are performed as necessary. Thus, a polymer film laminate 1 having a configuration suitable for practical use having the structure as shown in FIG. The removal of the spacer 30 may be performed, for example, by removing the spacer 30 from the surface of the stacked body 10, or may be performed by cutting and removing a region where the spacer 30 is formed in the stacked body 10.

  Moreover, the surface of the polymer film 4 in the polymer film laminate 1 may be polished as necessary, or may be treated with a chemical solution such as an acid or an oxidizing agent. In addition, treatments such as ultraviolet irradiation treatment and plasma irradiation treatment may be appropriately performed.

  According to the method for manufacturing the polymer film laminate 1 of the above-described embodiment, since the laminate 10 is wound by arranging the spacers 30 at both ends in the first step, the laminate 10 by winding. Winding can be performed while greatly reducing the contact between each other, and a roll of the polymer film laminate 1 with less adhesion between the adjacent laminates 10 can be obtained. As a result, it is possible to obtain a good polymer film laminate 1 with less deformation and deterioration of characteristics due to adhesion of the polymer film 4 part.

  In addition, since the spacer 30 in the present embodiment is composed of a wire mesh having the convex portion 32 and the convex portion 34, the stack 30 is wound up by the apparent thickness formed by the convex portion 32 and the convex portion 34. The bodies 10 can be separated from each other. Conventionally, in the case of using a wire net without unevenness, in order to surely suppress the adhesion of the laminated body 10, it was necessary to use one that actually has a thickness equivalent to the above apparent thickness. In the form, since a sufficient apparent thickness can be secured by forming the convex portions 32 and 34, a wire mesh that is significantly thinner than this can actually be used as a constituent material of the spacer. As a result, the spacer 30 can be significantly reduced in weight and heat capacity.

  Therefore, in this embodiment, by using such a spacer 30, in the heat treatment of the wound body 100, the loss of heat due to the spacer 30 is reduced, and the heat amount and time required for the heat treatment are reduced, resulting in high productivity. Can be achieved. Furthermore, since the heat capacity of the spacer 30 is small, it is difficult to cause a difference in the degree of heat treatment between the outer peripheral portion and the inner peripheral portion of the wound body, thereby making it possible to obtain a homogeneous polymer film laminate. Become.

  In particular, when the spacer 30 having a shape in which the convex portions 32 and the convex portions 34 protruding on the opposite side are alternately provided as in the above-described embodiment, the thickness is obtained without forming any irregularities. As a result, the weight will be significantly reduced compared to spacers that are made larger. Therefore, the productivity of the polymer film laminate 1 can be improved extremely well.

  As mentioned above, although preferred embodiment of the polymer film laminated body of this invention and its manufacturing method was described, this invention is not limited to embodiment mentioned above, It can change suitably. For example, in the above-described embodiment, the spacer 30 is provided with the convex portions 32 and the convex portions 34 that alternately protrude on the opposite side. Instead of the shape, there may be used one having a predetermined reference surface and repeatedly forming protrusions formed so as to protrude from the reference surface to at least one side.

  Here, FIG. 5 is a diagram partially showing the planar shape of the spacer having a protruding portion protruding from the reference surface, and FIG. 6 is a schematic cross-sectional configuration taken along line VI-VI of the spacer shown in FIG. FIG. The spacer 32 shown in the figure is regularly and repeatedly provided with a convex portion 36 protruding with respect to the reference surface S. In such a spacer 32, the distance h between the top portion (top surface) of the convex portion 36 and the reference surface S is the apparent thickness of the spacer.

  In the manufacturing method of the above-described embodiment, the spacer 30 is disposed on the precursor layer 14 in the stacked body 10. However, the present invention is not limited to this, and the spacer 30 is arranged in such a manner that the precursor layer 14 in the stacked body 10 is The thickness can be appropriately changed as long as it does not come into contact with the metal foil 2 of the laminated body 10 that is adjacent to each other by winding.

  Specifically, for example, when the formation region of the spacer 30 is cut after heat treatment or the like, the precursor layer 14 is formed in the formation region of the spacer 30 in order not to waste the material for the polymer film 4. It does not have to be. In this case, the apparent thickness of the spacer 30 needs to be made as thick as the precursor layer 14 as compared with the above-described embodiment. Moreover, in embodiment mentioned above, although the laminated body 10 was wound up so that the precursor layer 14 might become inside, it is not limited to this, You may wind up so that the metal foil 2 may become inside. Even in these cases, the laminated body adjacent in the circumferential direction by the apex of the convex portion and the non-forming surface of the convex portion in the spacer 30, or the top portion of the first convex portion and the top portion of the second convex portion. Since 10 are sufficiently separated from each other, the precursor layer 14 can be prevented from coming into contact with the adjacent stacked body.

  Further, the spacer is not necessarily arranged so as to be aligned with the side of the end portion of the laminate, and may be protruded from the end portion of the laminate as long as it can be sandwiched between the laminates by winding. On the contrary, as long as the yield of the polymer film laminate is not extremely reduced, the polymer film laminate may be disposed inside the end of the laminate.

  In addition, the polymer film laminated body 1 obtained by the manufacturing method mentioned above is not restricted to what has the two-layer structure of the metal foil 2 and the polymer film 4, You may have another layer suitably. .

  Since the polymer film laminate of the present invention having the above-described configuration has characteristics such as high flexibility, stable dimensions, and less warpage, it can be applied to various applications. For example, base films for copper-clad laminates, multi-layer printed circuit board films for semiconductor packages and motherboards by the build-up method, flexible printed wiring board (FPC) films, tape automated bonding films, tag tape films , A packaging film for heating a microwave oven, a film for electromagnetic wave shielding, and the like.

  Especially, a polymer film laminated body is preferably applied as a film for FPC mounted in an electronic device from the above-mentioned characteristics. As FPC using the polymer film laminate of the present invention, for example, a metal foil 2 in the polymer film laminate 1 was processed into a circuit, and a circuit was formed on a substrate made of the polymer film 4. The thing which has a structure is mentioned.

  Here, FIG. 7 is a diagram illustrating an example of a cross-sectional configuration of the FPC. The FPC 300 includes a substrate 22 and a circuit 24 formed on the substrate 22. The substrate 22 is composed of the polymer film 4 in the polymer film laminate 1, and the circuit 24 is formed by processing the metal foil 2 in the polymer film laminate 1. When used for FPC applications, it is preferable that the polymer film has a thickness of 10 μm or more because it can exhibit high insulation.

  The polymer film laminate of the present invention has excellent high frequency characteristics and low water absorption, particularly when the polymer film is composed of liquid crystal polyester. Therefore, in this case, the polymer film laminate can be suitably used for uses such as a high-frequency printed wiring board, a high-frequency cable, a communication device circuit, and a package substrate.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Manufacture of laminates]

  First, the manufacturing method of the laminated body used by a following example and a comparative example is demonstrated. That is, first, in a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction pipe, a thermometer and a reflux condenser, 941 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 273 g of 4-aminophenol ( 2.5 mol), 415.3 g (2.5 mol) of isophthalic acid, and 1123 g (11 mol) of acetic anhydride. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and this temperature was maintained and refluxed for 3 hours.

  Next, the temperature was raised to 320 ° C. over 170 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. And the time when the increase in torque was recognized was regarded as the end of the reaction, and the contents in the reactor were taken out. The solid content obtained from the contents was cooled to room temperature, pulverized with a coarse pulverizer, and then held at 250 ° C. for 10 hours in a nitrogen atmosphere to cause a polymerization reaction in a solid phase, thereby producing a liquid crystalline polyester powder. Got.

  Then, 200 g of the obtained liquid crystal polyester powder was added to 1170 g of N-methyl-2-pyrrolidone, which was heated to 180 ° C. and completely dissolved to obtain a brown transparent solution. To this solution, 48.7 g of aluminum borate (Shikoku Kasei Kogyo Co., Ltd., Arborex M20C) was added as an inorganic filler to obtain a solution composition containing liquid crystal polyester.

Thereafter, the obtained solution composition was placed on an electrolytic copper foil (3EC-VLP, width 280 mm, thickness 18 μm, manufactured by Mitsui Kinzoku Co., Ltd.) using a slot die coater, and the resin layer thickness after heat treatment was 25 μm. Cast to become. Then, by heating at 120 ° C. using a high-temperature hot air dryer, the solvent in the applied solution composition is removed until the residual solvent amount is 18% by weight or less, and the polymer film precursor is removed. A precursor layer was formed. In this way, the laminated body provided with a precursor layer on electrolytic copper foil was obtained.
[Manufacture of polymer film laminate]

Example 1
The laminate described above was wound up 3 m around a SUS316 tube having an outer diameter of 89.1 mm so that the copper foil side was the outside, and a wound body was obtained. At this time, spacers were arranged at both ends in the winding direction on the precursor layer side of the laminate, and the spacers were taken up together with the laminate. As the spacer, in an embossed wire mesh (nets101 Co., Ltd., 100 mesh plain woven wire mesh made of SUS304, a substantially quadrangular pyramid-shaped convex portion formed by punching on one side and the same shape formed by punching on the opposite side. A projection provided so that the projections are continuous with each other without interruption, a width of 50 mm, an apparent thickness of 1.4 mm, and a weight of 50 mm × 1 m: 25 g) was used.

  Then, the obtained wound body was put into a high temperature hot air dryer, and heat treatment was performed at 320 ° C. for 2 hours in a nitrogen atmosphere to obtain a roll wound with the polymer film laminate.

(Example 2)
As a spacer, in the embossed wire mesh (nets101 Co., Ltd., 200 mesh plain woven wire mesh made of SUS304, a substantially quadrangular pyramid-shaped convex portion that is formed on one side and a convex portion of the same shape that is formed on the opposite side. Polymer film in the same manner as in Example 1 except that a portion having a width of 50 mm, an apparent thickness of 1.2 mm, and a weight of 50 mm × 1 m: 12 g) was used. A roll on which the laminate was wound was obtained.

(Comparative Example 1)
The same as in Example 1 except that a plain woven wire mesh (made of SUS304, wire diameter φ0.1 mm, 100 mesh, width 50 mm, thickness 0.18 mm, 50 mm × 1 m weight: 23 g) was used as the spacer. A roll on which the molecular film laminate was wound was obtained.

(Comparative Example 2)
As in Example 1, except that a plain woven wire mesh (made of SUS304, wire diameter φ0.23 mm, 50 mesh, width 50 mm, thickness 0.37 mm, weight 50 mm × 1 m: 49 g) was used as the spacer. A roll on which the molecular film laminate was wound was obtained.

(Comparative Example 3)
As a spacer, using a single twist woven wire mesh (made of SUS304, wire diameter φ0.12 mm × 7 twists / 0.35 mm, 30 mesh / 30 mesh, width 80 mm, thickness 0.75 mm, weight 80 mm × 1 m: 127 g) A roll with the polymer film laminate wound thereon was obtained in the same manner as in Example 1 except that the winding was performed while arranging the stranded wires along the winding direction.

(Comparative Example 4)
As the spacer, a twisted woven wire mesh (made of SUS304, wire diameter φ0.23 mm × 7 twists / 0.7 mm, 10 mesh / 10 mesh, width 80 mm, thickness 1.4 mm 80 mm × 1 m, weight: 172 g) is used. A roll with the polymer film laminate wound thereon was obtained in the same manner as in Example 1 except that the film was wound while being arranged along the winding direction.
[Evaluation of adhesion of polymer film laminate]

In the rolls of polymer film laminates obtained by the production methods of Examples 1-2 and Comparative Examples 1-4, it was confirmed whether adhesion between polymer film laminates occurred. The obtained results are shown in Table 1. In Table 1, the case where adhesion did not occur was indicated as “good”, and the case where adhesion occurred was indicated as “adhesion”. In the table, the apparent thickness is shown for the examples as the spacer thickness.

From Table 1, in Examples 1 and 2 using the embossed wire mesh in which convex portions are formed so as to have a predetermined apparent thickness as spacers, adhesion is surely prevented even though the spacers are sufficiently light. I was able to. On the other hand, in Comparative Examples 1 to 4 using a normal wire mesh, a sufficient thickness could not be secured in Comparative Examples 1 and 2 using a light wire mesh, and the laminates adhered, and in Comparative Examples 3 and 4, it was thick. Adhesion could be prevented because of the use of a spacer, but the weight of the spacer was very large compared to the examples.
[Evaluation of temperature of wound body during heat treatment]

(Reference Example 1)
An electrolytic copper foil (3EC-VLP, width 280 mm, thickness 18 μm, manufactured by Mitsui Kinzoku Co., Ltd.) is wound on a SUS316 tube having an outer diameter of 89.1 mm and a wall thickness of 5.5 mm for 30 m to wind the wound body temperature. A body sample was obtained. At this time, the embossed wire mesh used in Example 1 was disposed as a spacer at both ends of the copper foil, and this was wound up together with the copper foil.

(Comparative Reference Example 1)
Winding body sample in the same manner as in Reference Example 1 except that the single twisted woven wire mesh used in Comparative Example 3 was used as the spacer and winding was performed while the twisted wire was placed along the winding direction. Got.

(Evaluation)
About the obtained winding body sample, after inserting a thermocouple in the innermost periphery and the outermost periphery, vertically placed in a tank of a clean oven (CLO-21CH-S type manufactured by Koyo Thermo System Co., Ltd.) A temperature program for sequentially performing nitrogen substitution (30 ° C. × 30 minutes), temperature increase (2 hours), holding at 320 ° C. (12 hours), and cooling was sequentially performed. And the temperature profile of the innermost periphery part of a roll and the outermost periphery part in the winding body sample in this case was recorded.

  The temperature profile obtained with the wound body sample of Reference Example 1 is shown in FIG. 8, and the temperature profile obtained with the wound body sample of Comparative Reference Example 1 is shown in FIG. Moreover, the chart which evaluated the temperature difference by the place of a roll by (roll inner peripheral part temperature-roll outer peripheral part temperature) is shown in FIG.

  8 to 10, the reference example 1 using the embossed wire mesh as the spacer has a faster follow-up of the roll temperature with respect to the furnace temperature than the comparative reference example 1, and the temperature difference between the inner and outer peripheral portions of the roll is small. It was confirmed that it was possible.

It is a figure which shows typically the cross-sectional structure of the polymer film laminated body of suitable embodiment. It is a figure which shows typically the process of winding up a laminated body in a 1st process. It is a figure which shows partially the planar shape of the spacer 30 of suitable embodiment. It is a figure which shows typically the cross-sectional structure which follows the IV-IV line of the spacer 30 shown in FIG. It is a figure which shows partially the planar shape of the spacer of the shape where the convex part protruded from the reference plane. It is a figure which shows typically the cross-sectional structure which follows the VI-VI line of the spacer shown in FIG. It is a figure which shows an example of the cross-sectional structure of FPC. 4 is a graph showing a temperature profile obtained with the wound body sample of Reference Example 1. 4 is a graph showing a temperature profile obtained with a wound body sample of Comparative Reference Example 1. It is the chart which evaluated the temperature difference by the place of a roll.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Polymer film laminated body, 2 ... Metal foil, 4 ... Polymer film, 10 ... Laminated body, 14 ... Precursor layer, 30 ... Spacer, 32, 34, 36 ... Convex part, 22 ... Board | substrate, 24 ... Circuit 100 ... Winding body, 300 ... FPC.

Claims (5)

A first step of winding a laminate in which a precursor layer made of a precursor of a polymer film is formed on a metal foil to obtain a wound body;
Heat-treating the wound body to obtain a polymer film laminate in which a polymer film is formed on the metal foil, and
In the first step, spacers are arranged along the sides located at both ends in the direction intersecting the winding direction of the laminated body so as to be sandwiched between the laminated bodies to be wound up. Winding up
The spacer is composed of a wire net that is repeatedly formed on almost the entire surface, and is formed so as to protrude toward at least one surface side, and a surface connecting the top of the convex portion and the convex portion are formed. There use those apparent thickness represented by the distance between that are not surface is 0.5 to 3 mm,
The polymer film is composed of liquid crystal polyester,
The manufacturing method of the polymer film laminated body characterized by the above-mentioned. A first step of winding a laminate in which a precursor layer made of a precursor of a polymer film is formed on a metal foil to obtain a wound body;
Heat-treating the wound body to obtain a polymer film laminate in which a polymer film is formed on the metal foil, and
In the first step, spacers are arranged along the sides located at both ends in the direction intersecting the winding direction of the laminated body so as to be sandwiched between the laminated bodies to be wound up. Winding up
The spacer is composed of a wire mesh in which first protrusions and second protrusions which are formed so as to alternately protrude on the opposite side are repeatedly provided on substantially the entire surface, and the top of the first protrusion is There use those apparent thickness represented by the distance between the connecting it surface and the second connecting it faces the top of the protrusion is 0.5 to 3 mm,
The polymer film is composed of liquid crystal polyester,
The manufacturing method of the polymer film laminated body characterized by the above-mentioned.   The method for producing a polymer film laminate according to claim 1 or 2, wherein a material having an apparent thickness of 1 to 2 mm is used. The thickness of the said metal net itself is 50-600 micrometers, The manufacturing method of the polymer film laminated body as described in any one of Claims 1-3 characterized by the above-mentioned. The method for producing a polymer film laminate according to any one of claims 1 to 4, wherein the mesh of the wire mesh is 25 to 400 mesh.

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