TW201032999A - Flexible metal-clad laminate and a method of manufacturing the same - Google Patents

Abstract

Disclosed is a flexible metal-clad laminate. More specifically, disclosed is a flexible metal clad laminate including: a first polyimide layer that is positioned on one surface of a metal foil and has glass transition temperature of 300 to 500 DEG C; a second polyimide layer that is positioned on one surface of the first polyimide layer and has a linear thermal expansion coefficient of 1 to 20 ppm/K; and a thermoplastic polyimide layer that is positioned on one surface of the second polyimide layer, whereby the flexible metal-clad laminate has an excellent exterior after imidization, is not curled after and before etching, and has excellent adhesive strength with a metal foil and excellent dimensional stability after etching.

Description

201032999 VI. Description of the Invention: [Technical Field] The present invention relates to a flexible metal-clad laminate and a method of manufacturing the same, and more particularly to a flexible coating for use in the manufacture of printed circuit boards Metal laminate and method of producing the same. [Prior Art] A flexible metal clad laminate is used for manufacturing a flexible printed circuit board which is a laminate of a conductive metal foil and an insulating resin, which can be processed by a microcircuit and can be bent in a narrow space. Therefore, the usability is improved, and the cover electronic component is developed in the direction of miniaturization and weight reduction. The flexible metal clad laminate can be divided into a two-layer type and a three-layer type. The three-layer type using the adhesive has problems of deterioration in the heat and the flammability, and the three-layer type has a problem of dimensional change during the heat treatment as compared with the two-layer type. Therefore, in the manufacture of flexible printed circuit boards, compared to the three-layer type, the current trend is generally to use a two-layer type flexible metal-clad laminate. Since the current trend is toward light, thin, and miniature circuit boards, the use of double-sided metallized laminates is improved, and the double-sided metallized laminate is typically laminated by using a thermoplastic polyimide. The outermost layer of the polyimide layer of the layer and the metal foil are produced. In this case, the flexible copper-clad laminate may be bent after and after etching due to the presence of the thermoplastic polyimide resin. Korean Patent Publication No. 10-2004-0084028 and No. 2006-0129081, or No. 2003-0079991 disclose several methods of applying and drying a polyimide film precursor resin to improve adhesion to a metal foil. Strength and control of the bending after and after etching the metal layer. These methods of exposure employ thermoplastic polyimine (-TPI) as the 201032999 polyimine resin which is applied directly to the metal foil to maintain the bond strength to the applied metal foil. However, in the Korean Laid-Open Patent Publication No. 10-2004-0084028, there are problems in appearance defects such as foaming of the surface of the polyimide and the interlayer of the polyimide film or the layer of the polyimide resin and the metal foil. Layers, etc., because the thermoplastic polyimide resin in contact with the metal foil typically has a low glass transition temperature (Tg) of about 200 to 250 °C. Korean Patent Publication No. 2006-0129081 requires a thin thermoplastic polyimide layer to match the linear thermal expansion coefficient of the polyimide resin with the linear thermal expansion coefficient of the metal, and the Korean Patent Publication No. 2003-0079991 increases the high heat. © Use of plastic polyimine. SUMMARY OF THE INVENTION [Technical Problem] In order to solve the problems as described above, it is an object of the present invention to provide a flexible metal-clad laminate which has an excellent appearance after the ruthenium reaction. It does not cause bending after etching and before, and has excellent bonding strength and dimensional stability between the polyimide film and the metal foil after etching. Further, another object of the present invention is to provide a metallized laminate which can be used as a double-sided metal-clad laminate by laminating a single-sided metal-clad laminate and a metal foil, and Production method. [Technical Solution] In order to achieve the above object, the present invention provides a flexible metal-clad laminate comprising: a first polyimide layer on a surface of a metal foil and having 300 to a glass transition temperature of 500 ° C; a second polyimide layer on one surface of the first polyimine layer 201032999 and having a linear thermal expansion coefficient of 1 to 20 ppm/K; and a thermoplastic polysiloxane An amine layer is on the surface of one of the second polyimide layers. The present invention provides a method of making a flexible metal laminate comprising: (a) applying and drying a polyaminic acid solution on a surface of a metal crucible and in the quinone After the reaction, the glass transition temperature of 300 to 500 ° C is followed by formation of a first polyimine layer; (b) application and drying of a polyaminic acid solution, the polyamic acid solution is located in the formed a surface of one of the polyimine layers having a linear thermal expansion coefficient of 1 to 20 ppm/K after the oxime imidization reaction, followed by formation of a second polyimine layer; (c) application and drying of the polyamidamine An acid solution, the polyaminic acid solution is located on a surface of one of the formed second polyimide layers and has a glass transition temperature of 200° CS Tg S 300° C. and 30 to 200 after the oxime imidization reaction a linear thermal expansion coefficient of ppm/K, followed by formation of a thermoplastic polyimide layer; and (d) heat treatment at 0 to 500 ° C to imidize the resulting laminate. In the following, an exemplary embodiment of the invention will be described in detail, and in the description of the invention, related known functions or structures will be omitted to avoid obscuring the object of the invention. In the present specification, "about", "substantially", etc., are expressed as a degree of vocabulary as a numerical value, or a meaning that approximates the numerical value when the above-mentioned meaning occurs within the inherent tolerance of the preparation process and the material. It is used to prevent inappropriate use of the infringer. The precise or absolute values mentioned herein are intended to aid the understanding of the present invention. The present invention relates to a flexible metal-clad laminate comprising: a 7-polyimine layer (hereinafter referred to as "first polyimine layer") on a surface of a metal foil and having 300 to a glass transition temperature (Tg) at 500 ° C; a polyimine layer (hereinafter referred to as 201032999 "second polyimine layer") on the surface of one of the first polyimine layers described above and having a linear thermal expansion coefficient of 1 to 20 ppm/K, wherein a 3-thermopolyimine resin layer (hereinafter referred to as "thermoplastic polyimide layer") is present on one surface of the second polyimine layer, and via the layer A double-sided flexible metal clad laminate obtained by combining the above flexible metal-clad laminate with another metal foil. The laminate according to the present invention has an excellent appearance after the thermal imidization reaction, does not bend after and after etching, and has excellent adhesion between the polyimide layer and the metal foil after etching. Strength and dimensional stability. Further, the layer according to the present invention can be formed by laminating another metal foil on one surface of the thermoplastic polyimide layer to produce a double-sided metal clad laminate. The first polyimine layer on the surface of one of the metal foils has a linear thermal expansion coefficient of 5 to 40 ppm/K. Preferably, the first polyimide layer has a higher linear coefficient of thermal expansion in the range of 5 to 25 ppm/K as compared to the second polyimide layer. In this case, the bonding strength with the applied metal foil can be stably maintained at at least 1.0 kgf/cm, more preferably 1.0 to 3.0 kgf/cm, and because the second polyimine layer has a linear thermal expansion coefficient. The difference formed by the above is the bending stress of the foil, which can eliminate the bending of the laminate due to the thermoplastic polyimide layer (having a high linear thermal expansion coefficient). As the first polyimide layer in contact with the metal foil, a polyimide resin having a glass transition temperature of 300 ° C or more, more preferably 300 to 500 ° C, is used. In general, the thermoplastic polyimide resin is used as the first polyimide layer, and in this case, there is a problem of appearance defects due to a low glass transition temperature, such as foaming and aggregation of the polyimide surface. Debonding between the quinoneimine resin layers or between the polyimide layer and the metal foil. Therefore, in order to prevent appearance defects during the polyimidization process, 201032999 should use a low thermal expansion polyimine resin having a glass transition temperature of 30 (TC or higher) as the first polyimide in contact with the metal foil. A layer of the second polyimine layer on the surface of one of the first polyimide layers having a linear thermal expansion coefficient of 20 ppm/K or less, more preferably 1 to 20 ppm/K. The high linear thermal expansion coefficient of the imine should use a polyimine resin having a low linear thermal expansion coefficient as the second polyimine layer, which makes the linear thermal expansion coefficient of the overall polyimine resin similar to the linear thermal expansion coefficient of the metal foil. "In this way, the laminate is prevented from bending after etching and before and the dimensional change after etching can be controlled at -0.1% to +0.1%', preferably -0.05% to +0.05%. The composition of the amine layer or the second polyimide layer can exhibit a generally low thermal expansion, and any composition can be used. As a raw material of the polyimine layer as described above, tetracarboxylic dianhydride (tetracarboxylic acid) can usually be used. Acid dianhydride) a diamino compound, but the raw material is not limited thereto. As the tetracarboxylic dianhydride exhibiting low thermal expansion, pyromellitic dianhydride, 3, 3, 4 is preferably used. 4,-biphenyltetracarboxylic acid dianhydride (3,3',4,4'-biphenyltetracarboxylic acid dianhydride) and 3,3',4,4'·diphenylmethylamine tetrahydro acid (3,3,, 4,4'_benzophenonetetracarboxylic acid dianhydride. Further, as the diamine compound, 4,4'-diaminophenyl ether, p-phenylenediamine or p-phenylenediamine is preferably used. And 4,4'-thiobisbenzenamine, etc. The low thermal expansion of the polyamidene resin according to the present invention comprises the polyimine resin of the following Chemical Formula 1. 201032999 [ In the chemical formula 1], all of the components of the chemical formula 1 are 0.5 S m S 1.0 and 0 S η S 0.5, m + n = 1. The X and Y groups in Chemical Formula 1 are independently derived from a fragrance selected from the following structures. a tetravalent portion of a dianhydride compound.

Also, if the composition of the thermoplastic polyimide resin has sufficient fluidity at at least the glass transition temperature, any composition can be used. Further, a composition that is fluid through pressure can be used. Furthermore, it also comprises a thermoplastic polyimide resin made of a minimum of two two-needle monomers and at least two kinds of diamine monomers, and a thermoplastic made from a single dianhydride monomer and a single diamine monomer. Polyimine resin. The thermoplastic polyimide layer of the present invention may have a glass transition temperature of 200 ° C S Tg S 300 ° C and a linear thermal expansion coefficient of 30 to 200 ppm / K. More specifically, the thermoplastic polyimide layer formed from the thermoplastic polyimide resin of the present invention preferably contains 30 to 100% of repeating units including W and Z in the following Chemical Formula 2 (hereinafter referred to as "thermoplastic repeating unit" "). When the fraction of the thermoplastic repeating unit is less than 30%, the flowability of the thermoplastic polyimide layer is insufficient, so that it cannot be thermally laminated, or after the double-sided metallized laminate is produced and the laminated metal Low bonding strength. Because 9 201032999, the fraction of thermoplastic repeating units should be carefully controlled in consideration of the glass transition temperature of the thermoplastic polyimide layer. When considering the lamination process for producing a double-sided metal-clad laminate, the glass transition temperature of the thermoplastic polyimide resin is preferably about 200 to 300 〇C. [Chemical Formula 2]

In the above Chemical Formula 2, m and n are real numbers and m + n = 1, 0.3 g m $ 1.0, 0 ^ η ^ 0.7. The W in the above Chemical Formula 2 is a divalent moiety derived from an aromatic diamine compound selected from the group consisting of, respectively, or copolymerized with each other:

Wi is selected from the group consisting of: -(CH2)-, _(Cli2)p- (P is an integer selected from 2 to 1 )), -CH2-C(CH2)2-CH2-;

-(CH2)-; 10 201032999 w4 is selected from: -0--CO-; W5 is selected from: -Ο-, -CO-, -S-, -S02-, -C(CH3)2-,- CONH-, -C(CF3)2-, W6 are selected from -O-, -CO-, -S-, -S02-, -C(CH3)2-, -CONH-, -C(CF3)2_, And -(CH2)-. More preferably, W in the above Chemical Formula 2 is a divalent moiety derived from an aromatic diamine compound selected from the following, which is used alone or by copolymerization with each other:

W3, w5 and w6 are selected from: -o-, -co-, -s-, -so2-, -c(ch3)2-, -conh-, -c(cf3)2-, -(ch2)_ The Z system in the above Chemical Formula 2 is a tetravalent moiety derived from an aromatic dianhydride selected from the following, which is used alone or by copolymerization with each other:

The P group in the above Chemical Formula 2 is a divalent moiety derived from an aromatic diamine compound selected from the following, which is used alone or by copolymerization with each other:

11 201032999

Pi is a group selected from -Ο-, -CONH-; p2 is a group selected from -Η, -CH3, -CF3; Q of the above Chemical Formula 2 is derived from the following derived from aromatic two The tetravalent portion of the anhydride, which is used alone or via copolymerization with each other:

The polyimine resin described in the present invention contains all the resins of the above-described sulfonium amine ring of the following Chemical Formula 3, but is not limited thereto. Examples of the polyimine resin may include polyimine, polyamidimide, polyesterimide, and the like. [Chemical Formula 3]

In Chemical Formula 3, Ar and Ah are a (C6 to C20) aromatic group, wherein - is selected from a real number of from 1 to 1000, 0000. However, if the desired characteristics of the present invention can be attained, the composition of the polyimide resin is not particularly limited and may be a single polyimide resin, a derivative thereof or a mixture of at least a polyimide resin and a derivative thereof. Composed of. Further, an anthraquinone promoter such as pyridine and quinoline, a adhesion promoter such as a decane coupling agent, a titanate coupling agent, an epoxy compound, etc., an antifoaming agent which contributes to the application process, and other additives such as an anti-foaming agent such as pyridine and quinoline may be used. Leveling agent, etc. 12 201032999 The present invention provides a method of making a flexible metallized laminate comprising: (a) applying and drying a polyaminic acid solution on a surface of a metal foil and After the imidization reaction, the glass transition temperature of 300 to 500 〇c is followed by formation of a first polyimine layer; (b) application and drying of the polyaminic acid solution. The polyamic acid solution is located at the institute. Forming a surface of one of the first polyimine layers and having a linear thermal expansion coefficient of i to 20 ppm/K after the hydrazide reaction, followed by formation of a second polyimine layer; (c) application and drying a polyaminic acid solution which is located on the surface of one of the formed second polyimide layers and has a glass transition of 200 ° C s Tg S 300 ° C after the hydrazide reaction Temperature and a coefficient of linear thermal expansion of 30 to 200 ppm/Κ, followed by formation of a thermoplastic polyimide layer; and (d) heat treatment of the resulting laminate at T to 50 (Tc) a laminate produced. In steps (a) to (c), prior to application as a polyimine The drying temperature after the polyamic acid solution of the resin is not limited, but is preferably from 8 to 22 (rc. The poly-aracine solution (after step (a) to step (c)) becomes a coating. A solid gel film with self-supportability on a copper plate. When the temperature of the dry polyamid solution is lower than the rib, the volatilization rate of the solvent is not significant, so it is difficult to substantially Show drying effect. On the other hand, when the drying temperature of the polyaminic acid solution is higher than 22 (rc, the coating layer will be excessively hardened, so there is a risk of lowering the physical properties thereafter or failing to exhibit stable physical properties. The present invention provides a flexible metal-clad laminate composed of a first polyimine layer, a second polyimide layer and a thermoplastic polyimide layer on one surface of a metal foil. The formation is formed by repeatedly applying and drying the polyimide precursor resin and then converting it to form a polyolefin resin by infrared heat treatment. 13 201032999 The polyimine resin contained in each layer can be directly used in complete Amination The state of the partially imidized state is applied to the metal town, but usually by applying a solution of the polyimide precursor solution and then performing a thermal or chemical conversion procedure. As the heat treatment method, any method can be applied, but usually The following heat treatment method: applying and drying a portion of the yttrium iodized polyimide resin or the poly-imine precursor resin to form a gel film' and thereafter subjecting the gel film to a preset in a drying oven The gel is thinly or continuously fed to the drying oven for a predetermined period of time to shape it. The heat treatment temperature is usually 3 ° C or higher. More preferably, 300 to 500 ° C is performed. High temperature treatment. _ A known heating method which satisfies the object of the present invention can be used as a secret method. A hot air heating furnace is usually used under a nitrogen atmosphere. However, in this case, there is a difference in the thickness direction in the development process of the imidization reaction, which makes it impossible to carry out the heat treatment of the uniform sentence, and in the case of a thick film, it is difficult to exist. - Solvent removal in the film results in poor dimensional stability. Therefore, in order to perform this issue _

The heat treatment of the laminate is preferably carried out by using an infrared heater, whereby uniform heat treatment can be performed in the thickness direction of the crucible; thereby, a flexible metallized laminate having excellent dimensional stability can be produced. Its dimensional change after etching is 〇I. 〆 Q +0.1% ' is preferably -0.05% to +0.05%. As a suitable coating method to be applied to each layer of the present invention, a doctor blade method, a roller coating method, a die coating method, a curtain coating method, a knife coating method, and the like may be used. However, The method for satisfying the object of the present invention is not limited thereto. The double-sided metallized laminate described in the present invention can be produced via an additional layer of human but metal foil in a thermoplastic polyimide layer. The lamination temperature is not special, and the new one must be heated at the temperature of the transition temperature of the thermoplastic polyimide resin. The temperature is high. 14 201032999 When the heating temperature of the thermoplastic polyimide is not enough, it cannot be guaranteed. The sufficient fluidity required for the metal foil to be pressed, so that a stable bonding strength cannot be ensured. Preferably, the heat treatment temperature at the time of pressing is usually 30 to 100 ° C higher than the glass transition temperature (Tg) of the thermoplastic polyimide film. Further, the lamination pressure is preferably a linear pressure of 50 to 200 kgf/cm. When the pressure is raised, the lamination temperature can be lowered, so that work is performed as much as possible under high pressure. The present invention provides a flexible metal clad laminate having a peel strength of 1.0 to 3.00 kgf/cm in the interface between the first polyimide layer and the metal foil. In addition, the present invention provides a flexible metallized laminate having a thickness of from 1 〇 to 3.0 kg in the interface of the thermoplastic polyimide layer and the metal foil stacked thereon (via performing further lamination) The peel strength of force/cm can stably maintain the bonding strength. Advantageous Effects As described above, the flexible metal-clad laminate according to the present invention has an excellent appearance after the imidization reaction, does not bend after etching, and is excellent with metal foil. Bond strength. Further, the laminate produced according to the present invention can be produced as a double-sided metal-clad laminate via a lamination process. The above and other objects, features and advantages of the present invention will become apparent from [Bottom of the Invention] Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the invention is not limited thereto. The abbreviations used in the following examples are as follows: 15 201032999 -DMAc: N,N-dimethylacetamide -BPDA: 3,3',4,4,-biphenyltetracarboxylic acid II (3,3,4,4,4-biphenyl tetracarboxylic acid dianhydride) -PDA: p-phenylenediamine -ODA: 4,4'diaminodiphenylether -TPE -R: 1,3 · bis(4-aminophenoxy)benzene -BAPB: 4,4'-bis(4-aminophenoxy) Benzene (4,4'-bis(4-aminophenoxy) biphenyl). The physical properties disclosed in the present invention are as follows: 1. Measurement of linear thermal expansion coefficient (CTE) and glass transition temperature (Tg) The temperature is raised to a maximum of 4 〇〇eC at a rate of 5 ° C per minute, and the thermal expansion value between l ° ° C and 250 ° C is measured and averaged by using a thermomechanical analyzer (TMA). And get. Further, the turning point of the thermal expansion curve measured by the above method is regarded as the breaking transition temperature (Tg). 2. The curvature after etching and before is the measurement of the laminate after the moment and before the song 'cut each sample into a square of 3 cm length and width and measure the height of each corner from the ground and take the average. When the average value does not exceed 1 cm, it is regarded as a flat laminate. 3. The bonding strength between the polyimide resin and the metal foil is to measure the bonding strength between the polyimide resin and the metal foil, and the metal layer of the laminate is patterned into a width of 1 gong' after using one million energy The universal testing machine (UTM) was tested at 18 〇. Peel strength. 201032999 4. The appearance of the polyimide resin was observed by observing the surface morphology of each of the laminates which were cut into 3G cm squares, when there was no foaming, swelling, and between the layers of the polyimide resin layer. When the layer of the polyimide resin layer and the metal foil are not delaminated, it is judged that the appearance of the surface of the resin is good. 5. Dimensional change after the engraving According to the method of IPC-TM-650, 2.2, 4Β. After drilling the position-recognizing holes at the four end points of each square sample (longitudinal (MD) and transverse (TD) lines 275 X 255 mm), store at 23. (: and 50% relative humidity (RH) constant temperature and humidity device for 24 hours, measure the distance between each hole three times and take the average. After that, etch the metal foil and store it in the constant temperature and humidity device for 24 hours. In the hour, the distance between the holes was measured again, and the measured lateral and longitudinal changes were calculated. [Preparation Example 1] The diamine (12,312 g of 〇8 and 2,533 g of 〇1^) was mixed and completely dissolved in In a 211,378 g DMAc solution, dianhydride (a total of 38'0 g of BpDA) was added in batches. Thereafter, the stirring was continued for about 24 hours to prepare a polyaminic acid solution. The prepared polyaminic acid solution was coated to prepare a film and heated to a maximum of 35 〇t for 60 minutes and maintained at this temperature for about 30 minutes. The thickness of the mash after curing was 20 microns. The glass transition temperature and the coefficient of linear expansion were 12.0 ppm/K. [Preparation Examples 2 to 8] The polyamine solvent solution was prepared in the same manner as in Preparation Example 1, using the compositions and contents as listed in Table 1. 17 201032999 [Table i] \ dianhydride Diamine 1 Diamine 2 DMAc Linear Thermal Expansion Coefficient (CTE, ppm/K) Tg (°C) Preparation Example 1 BPDA, 38,000 g PDA, 12,312 g ODA, 2,533 g 211,378 g 12.0 342 Preparation Example 2 BPDA, 12,000 g PDA, 3,063 g ODA, 2,431 g 117,072 g 24.1 323 Preparation Example 3 BPDA, 7000 g PDA, 2,380 g ODA, 232 g 33,108 g 9.8 351 Preparation Example 4 bpdaT^ 14,000 g PDA, Ί 4,032 g ODA, 1 1, 866 g 82,063 g 13.3 321 Preparation Example 5 BPDA, 3,300 g PDA, 606 g TPE-R, 1,639 g 38,227 g 40.7 234 Preparation Example 6 BPDA, 757 g BAPB 948 g - 11,572 g 65.11 259 Preparation Example 7 BPDA, 2,800 g TPE-R 2782 g - 38,475 g 50.8 232 Preparation Example 8 BPDA, 1,500 g ODA, 1021 g - 22,688 g 47.3 281 Example 1. The polyglycine solution prepared in Preparation Example 2 was applied to A 12 μm thick electrodeposited copper foil (surface roughness 'Rz=2.〇micron)' is dried at 13 ° C to form a first polyimine precursor Floor. The polyamic acid solution prepared in Preparation Example 3 was applied to the surface of the first polyimine precursor layer, followed by drying at 150 ° C to form a second polyimideimide precursor layer. Thereafter, the polyamic acid solution prepared in Preparation Example 8 was applied to the surface of the second polyimideimide precursor layer, followed by drying at 丨50 (: to form a thermoplastic polyimide intermediate layer). Thereafter, the above laminate is in a nitrogen atmosphere at a temperature of from 150 ° C to 395. (: a heat treatment for 9 minutes is carried out to make the alkalization of the element. After the ripening, the first - 醯The thickness of the imine layer, the second polyimide layer, and the thermoplastic polyimide layer were 5 18 201032999 microns, 13 microns, and 3.5 microns, respectively. These results are disclosed in Table 2. Example 2 Preparation Examples 2 prepared polyaminic acid solution was applied to a 12 micron thick electrolytically deposited copper foil (surface roughness, Rz = 2.0 microns), and then dried at 160 ° C to form a first polyimine precursor The polyamic acid solution prepared in Preparation Example 3 was applied to the surface of the first polyimideimide precursor layer, followed by drying at 150 ° C to form a second polyimideimide precursor layer. After the hydrazine, the poly-proline solution prepared in Preparation Example 7 is applied to the second polymerization. The surface of the imine precursor layer is then dried at 150 ° C to form a thermoplastic polyimide precursor layer. Thereafter, the above laminate is in a nitrogen atmosphere at 150 ° C to 395 ° C. After 9 minutes of heat treatment, it is completely imidized. After the aging, the thickness of the first polyimine layer, the second polyimide layer and the thermoplastic polyimide layer are respectively 5 micrometers. 13 μm and 3 μm. The results are disclosed in Table 2. Example 3 The polyamic acid solution prepared in Preparation Example 2 was applied to an electrodeposited copper foil having a thickness of 12 μm (surface roughness, Rz = 2.0 μm), followed by drying at 160 ° C to form a first polyimine precursor layer. The polyphthalic acid solution prepared in Preparation Example 3 was applied to the first polyimideimide precursor layer. On the surface, it was then dried at 150 ° C to form a second polyimideimide precursor layer. Thereafter, the polyamic acid solution prepared in Preparation Example 6 was applied to the second polyimine precursor. On the surface of the layer, then dried at 160 ° C to form a thermoplastic 19 201032999 The yttrium imide precursor layer. Thereafter, the above laminate is subjected to a heat treatment at 150 ° C to 395 ° C for 10 minutes in a nitrogen atmosphere to completely imidize the yttrium. The thickness of the polyimine layer, the second polyimide layer, and the thermoplastic polyimide layer were 5 microns, 13 microns, and 3 microns, respectively. These results are disclosed in Table 2. Example 4 Preparation of the preparation The polylysine solution prepared in Example 2 was applied to an 18 μm thick electrodeposited copper foil (surface roughness, Rz = 2.0 μm), and then dried at 160 ° C to form a first polyimine. The precursor layer was applied to the surface of the first polyimideimide precursor layer, followed by drying at 150 ° C to form a second polyimide precursor. Floor. Thereafter, the polyamic acid solution prepared in Preparation Example 5 was applied onto the surface of the second polyimide precursor layer, followed by drying at 150 ° C to form a thermoplastic polyimide precursor layer. Thereafter, the above laminate was subjected to a heat treatment at 150 ° C to 395 ° C for 10 minutes in a nitrogen atmosphere to completely imidize it. After aging, the first polyimine layer, the second polyimide layer, and the thermoplastic polyimide layer have thicknesses of 5 microns, 18 microns, and 3 microns, respectively. These results are disclosed in Table 2. Comparative Example 1 The polyamic acid solution prepared in Preparation Example 2 was applied to an electrodeposited copper foil having a thickness of 12 μm (surface roughness, Rz = 2.0 μm), followed by drying at 130 ° C. A first polyimine precursor layer is formed. The polyaminic acid solution prepared in Preparation Example 3 was applied to the surface of the first polyiminamide front 20 201032999 drive layer, followed by drying at 150 ° C to form a second polyimine precursor layer. . Thereafter, the above laminate was subjected to heat treatment at 150 ° C to 395 ° C for 19 minutes in a nitrogen atmosphere to be completely imidized. After aging, the thickness of the first polyimine layer and the second polyimide layer are 5 microns and 13 microns, respectively. These results are disclosed in Table 3. Comparative Example 2 The polyamic acid solution prepared in Preparation Example 4 was applied to an electrolytically deposited copper foil having a thickness of 18 μm (surface roughness, Rz = 2.0 μm), followed by drying at 150 ° C. To form a first polyimine precursor layer. The polyamic acid solution prepared in Preparation Example 7 was applied to the surface of the first polyimideimide precursor layer, followed by drying at 150 °C to form a second polyimideimide precursor layer. Thereafter, the above laminate was subjected to a heat treatment at 150 ° C to 395 ° C for 7 minutes in a nitrogen atmosphere to completely imidize it. After aging, the first polyimine layer and the second polyimide layer have thicknesses of 18 microns and 3 microns, respectively. The results of V and so on are disclosed in Table 3. Comparative Example 3 The polyamic acid solution prepared in Preparation Example 7 was applied to an electrolytically deposited copper foil having a thickness of 12 μm (surface roughness, Rz = 2.0 μm), followed by drying at 180 ° C. To form a first polyimine precursor layer. The polyamic acid solution prepared in Preparation Example 3 was applied to the surface of the first polyimideimide precursor layer, followed by drying at 150 °C to form a second polyimideimide precursor layer. 21 201032999 After that, the polyglycine solution prepared in Preparation Example 7 was applied to the surface of the second polyimideimide precursor layer, followed by drying at 150 ° C to form a thermoplastic polyimide precursor. Layer of matter. Thereafter, the above laminate was subjected to a heat treatment at 150 ° C to 395 ° C for 9 minutes in a nitrogen atmosphere, thereby completely hydrazating. After aging, the thickness of each of the first polyimide layer, the second polyimide layer, and the thermoplastic polyimide layer is 2 μm, 22 μm, and 2 μm, respectively. These results are disclosed in Table 3. Comparative Example 4 The polyamic acid solution prepared in Preparation Example 8 was applied to an electrolytically deposited copper foil having a thickness of 18 μm (surface roughness, Rz = 2.0 μm), followed by drying at 130 ° C. To form a first polyimine precursor layer. The polyamic acid solution prepared in Preparation Example 1 was applied onto the surface of the first polyimideimide precursor layer, followed by drying at 150 °C to form a second polyimideimide precursor layer. Thereafter, the polyphthalic acid solution prepared in Preparation Example 8 was applied to the surface of the second polyimideimide precursor layer, followed by drying at 180 ° C to form a thermoplastic polyimide film precursor layer. . Thereafter, the above laminate was subjected to a heat treatment at 230 ° C to 385 ° C for 24 minutes in a nitrogen atmosphere to completely imidize it. After aging, the first polyimide layer, the second polyimide layer, and the thermoplastic polyimide layer have thicknesses of 2.5 micrometers, 20 micrometers, and 3 micrometers, respectively. These results are disclosed in Table 3. 22 201032999 [Table 2] Example 1 Example 2 Example 3 Example 4 Metal foil and roughness (Illumination, Rz) Electrolytic copper foil thickness 12 micron roughness 2 micro semi-electrolytic copper foil thickness 12 micron roughness 2 micron Electrolytic copper foil thickness 12 micron roughness 2 micron electrolytic copper foil thickness 18 micron roughness 2 micron structure (thickness, micron) Preparation Example 2 / Preparation Example 3 / Preparation Example 8 (5/13/3.5) Preparation Example 2/ Preparation Example 3/Preparation Example 7 (5/13/3) Preparation Example 2 / Preparation Example 3 / Preparation Example 6 (5/13/3) Preparation Example 2 / Preparation Example 1 / Preparation Example 5 (5/18/3) Good bending before etching Good, good, good distortion after etching, good, good, good, good appearance after imidization reaction, good, good adhesion strength with copper foil (kg/min 1.0 1.1 1.0 1.0 Dimensional change after etching (MD/TD, %) 0.04/0.03 0.00/0.01 -0.01/-0.01 -0.01/-0.01 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparison Example 4 Metal foil and roughness (Illumination, Rz) Electrolytic copper foil thickness 12 micron roughness 2 micron electrolytic copper foil thickness 18 micron roughness 2 micron electrolytic copper foil thickness 12 micron coarse sugar 2 micron electrolytic copper foil thickness 18 micron roughness 2 micron structure (thickness, micron) Preparation Example 2 / Preparation Example 3/(5/13) Preparation Example 4 / Preparation Example 7 (18/3) Preparation Example 7 / Preparation Example 3 / Preparation Example 7 (2/22/2) Preparation Example 8 / Preparation Example 1/ Preparation Example 8 (2.5/20/3) The pre-etched copper foil is varnished inwardly to distort the resin. The etched copper foil is bent inwardly and the resin is inwardly curved. The appearance after the amination reaction is good, good, inferior and inferior. Fig. 1 is a photograph showing the appearance of the surface of the metal foil according to Example 1 of the present invention. Referring to Fig. 1, the appearance of the metal foil according to the present invention is good because it does not generate bubbles or swell, and there is no delamination between the polyimide layers or the polyimide layer and the metal foil. On the other hand, Fig. 2 is an appearance photograph of the surface of one of the metal foils according to Comparative Example 3. Referring to Fig. 2, a resin having a glass transition temperature of 23 201032999 of 232 ° C (less than 300 ° C) is used as the first polyimide layer, which generates bubbles on the surface of the metal foil, so that the appearance is not good. . The present invention has been described in terms of specific embodiments thereof, and those skilled in the art will readily appreciate that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph showing the appearance of the surface of a metal foil according to Embodiment 1 of the present invention. Fig. 2 is a photograph showing the appearance of the metal surface according to Comparative Example 3. [Main component symbol description] (none)

twenty four

Claims (1)

201032999 VII. Patent application scope: 1. A flexible metal-clad laminate comprising: a first polyimide layer on a surface of a metal foil and having a glass transition temperature of 300 to 500 ° C a second polyimide layer on the surface of one of the first polyimide layers and having a linear thermal expansion coefficient of 1 to 20 ppm/K; and a thermoplastic polyimide layer located in the second polymerization On one surface of the quinone imine layer. A flexible metal clad laminate according to claim 1, wherein another metal foil is further laminated on one surface of the thermoplastic polyimide layer. 3. The flexible metal clad laminate according to claim 2, wherein the peel strength of the interface between the thermoplastic polyimide layer and the metal foil is 1.0 to 3.0 kgf/cm. 4. The flexible metal-clad laminate according to claim 1, wherein each of the layers is formed by repeatedly applying and drying a polyamidene precursor resin, followed by infrared heat treatment. It is converted to a polyimide resin. 5. The flexible metal clad laminate of claim 1, wherein the first polyimide layer has a coefficient of linear thermal expansion of 5 to 40 ppm/K. 6. The flexible metallized laminate of claim 1, wherein the thermoplastic polyimide layer has a glass transition temperature of 200 ° C Tg S 300 ° C and a linear thermal expansion coefficient of 30 to 200 ppm / K. 7. The flexible metallized laminate of claim 1, wherein the peel strength of the interface between the first polyimide layer and the metal foil is 1.0 to 3.0 kgf/cm. 8. The flexible metallized laminate of claim 1, wherein the flexible gold-coated 25 201032999 sizing composition has a dimensional change after etching of -0.05% to +0.05%. 9. The flexible metal-clad laminate according to claim 5, wherein the resin forming the first polyimine layer or the second polyimide layer is represented by the following Chemical Formula 1: [Chemical Formula 1] ] Wherein, 0.5 S m $ 1.0 and 0 S n S 0.5, m+n=l; and X and Y in the chemical formula 1 are independently a tetravalent moiety derived from an aromatic dianhydride compound selected from the following structures, and each other The same or different: 10. The flexible metal-clad laminate according to claim 6, wherein the thermoplastic polyimide layer is a resin represented by the following Chemical Formula 2: Π匕学式2] In the above Chemical Formula 2, m and η are real numbers and m+n=l, 0.3 S m S 1·0, 0 ^ η ^ 0.7; 201032999 The W system in the above Chemical Formula 2 is derived from the following aromatic derived from A divalent moiety of an amine compound which is used alone or in copolymerization with each other: Wi is selected from the group consisting of -(CH2)-, -(CH2)P- (P system is selected from an integer from 2 to 10), -CH2-C(CH2)2-CH2-; W2 is selected from -Ο-, - CO-, -S-, -S〇2-, -C(CH3)2-, -CONH-, -C(CF3)2-, -(CH2)-; W3 is selected from -O-, -CO- , -S-, -S02-, -C(CH3)2-, -CONH-, -C(CF3)2-, -(CH2)-; w4 is selected from -〇-, -CO-; W5 From -O-, -CO-, -S-, -S02-, -C(CH3)2-, -CONH-, -C(CF3)2-, -(CH2)-; W6 is selected from -O- , -CO-, -S-, -S02-, -C(CH3)2-, -CONH-, -C(CF3)2-, -(CH2)-, the Z system in the above Chemical Formula 2 is selected from the following It is derived from the tetravalent portion of the aromatic dianhydride compound, which is used alone or via copolymerization with each other: 27 201032999 Wherein P in the above Chemical Formula 2 is a divalent moiety derived from an aromatic diamine compound selected from the following, which is used alone or by copolymerization with each other: Wherein Pi is a group selected from -0-, -CONH-; a group selected from -H, -CH3, -CF3; wherein Q of the above Chemical Formula 2 is selected from the following The fourth part of the price, which is used alone or in combination with each other: > The flexible metal-clad laminate according to claim 10, wherein W in the above Chemical Formula 2 is a divalent moiety derived from an aromatic diamine compound selected from the group consisting of the following, or copolymerized with each other And use: 28 201032999 Wherein W3, W5 and W6 are each selected from the group consisting of -〇-, *^〇-, _8_, -8〇2-, <(0:113)2-, -CONH-, -C(CF3)2-,- (CH2)-. 12. A method of making a flexible metallized laminate comprising: Ο ❹ (a) applying and drying a polyaminic acid solution on a surface of a metal foil and After the imidization reaction, a glass transition temperature of 30 〇 to 500 eC is formed to form a first polyimine layer; (b) applying and drying a polyamin amide solution, the poly lysine solution is formed therein a surface of one of the first polyimine layers having a linear thermal expansion coefficient of 1 to 20 PPm/K after the imidization reaction, followed by formation of a second polyamidene layer; (c) application and drying of the poly a proline solution, which is located on the surface of one of the second polyimine layers formed and has a glass transition temperature of 2°°C Tg S 300 C after the amination reaction And a linear thermal expansion coefficient of from 3 200 to 200 PPm/K, followed by formation of a thermoplastic polyimide layer; and (d) heat treatment at 〇炱5 ° C to imidize the resulting laminate A method of producing a flexible metal clad laminate according to claim 12, wherein the step is applied and The drying temperature of the dried polyaminic acid solution is 80 to 20 〇C. The method of manufacturing a flexible metal-clad laminate according to claim 12, wherein the coating method of each layer is a method selected from the group consisting of: a knife coating method, a roller coating method , a mold coating method, a curtain coating method, and a combination thereof. 15. The method of producing a flexible metal-clad laminate according to claim 12, wherein the heat treatment of the imidization of the produced laminate is performed by using an infrared heater under a nitrogen atmosphere. get on. 30