KR20160076879A - Double-sided flexible metallic laminate and method thereof - Google Patents

Abstract

The present invention relates to a double-sided flexible metallic laminate, and a manufacturing method thereof. More specifically, the present invention provides the method to manufacture the double-sided flexible metallic laminate, comprising: a step of preparing a double-sided flexible metallic laminate, including two metal layers opposite to each other among which a first polyimide layer, a second polyimide layer, the second polyimide layer and the first polyimide layer are arranged sequentially, and two single-sided flexible metallic laminated wherein the first polyimide layer and the second polyimide layer are arranged sequentially on a metal layer; and a step of performing lamination such that the second polyimide layers of the two prepared single-sided flexible metallic laminates are bonded to each other. The double-sided flexible metallic laminate has low permittivity and a low dielectric dissipation factor; and has excellent low hygroscopicity, high heat resistance, chemical resistance, dimensional stability, adhesion, and appearance uniformity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a double-sided flexible metal laminate,

More particularly, the present invention relates to a double-sided flexible metal clad laminate having a low dielectric constant polyimide layer and excellent heat resistance, chemical resistance, dimensional stability, adhesion and appearance uniformity. And a manufacturing method thereof.

2. Description of the Related Art In recent years, the speed of signal transmission between an electronic device and an external device has been rapidly increasing in accordance with the trend toward miniaturization, speedup, and various functions of electronic devices. Particularly, in recent years, there has been a demand for high-speed transmission of information according to high performance and high performance of electric / electronic apparatuses,

On the other hand, the flexible metal clad laminate is used as a base material for a flexible printed circuit board, and is also used as a surface heating element electromagnetic wave shielding material, flat cable, packaging material and the like. In accordance with recent trends, it has been required to develop an insulating layer having lower dielectric constant and dielectric loss factor than that of the conventional insulating layer.

Accordingly, a metal laminate including an insulating layer is used by using a polyimide resin having a specific structure, and an insulating material having a dielectric constant lower than that of polyimide, which is conventionally used as a material of the insulating layer, There has been an attempt to use Liquid Crystalline Polymer (LCP).

However, the above-mentioned LCP has a low heat resistance compared with the effect of lowering the dielectric constant, and has a problem that it is not compatible with the PCB manufacturing process which used polyimide in the past. Thus, recently, research for lowering the dielectric constant of conventional polyimide It is progressing.

An embodiment of the present invention is to provide a double-sided flexible metal clad laminate which is excellent in low hygroscopicity, high heat resistance, chemical resistance, dimensional stability, adhesive property and appearance uniformity while securing characteristics of low dielectric constant.

Another embodiment of the present invention seeks to provide a method for manufacturing the double-sided flexible metal clad laminate with simple and low cost.

According to an embodiment of the present invention, there is provided a semiconductor device comprising two metal layers opposed to each other,

A first polyimide layer between the two metal layers; A second polyimide layer; A second polyimide layer; And a first polyimide layer are sequentially arranged on the first polyimide layer.

Wherein the first polyimide layer is obtained by imidizing a solution of a first polyimide precursor obtained by reacting aromatic tetracarboxylic acid dianhydride with an aromatic diamine in the presence of a solvent,

At least one of the aromatic tetracarboxylic dianhydride and the compound contained in the aromatic diamine may be substituted with a fluorine atom.

The aromatic tetracarboxylic dianhydride may be selected from the group consisting of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane (6FDA), 2,2'- 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis [(dicarboxyphenoxy) phenyl] propane (Dicarboxyphenoxy) phenyl] propane, BSAA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ', 4,4'-benzotetracarboxylic dianhydride, BTDA), 4,4'-oxydiphthalic dianhydride (ODPA), 4,4' - (4,4'-iso (4,4 '- (4,4'-isopropylidenediphenoxy) -bis- (phthalic anhydride), BPADA), bicyclo [2.2.2] oct- -Ene-2,3,5,6-tetracarboxylic dianhydride (DCPD-DA), 3,4,3-tetracarboxylic dianhydride (bicycle [2.2.2] oct- ', 4'-diphenylsulfone tetracarboxylic (3,4,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, DSDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene 1,2-dicarboxylic anhydride (DTTDA), which is selected from the group consisting of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalen-1,2-dicarboxylic anhydride And may include one or more species.

The aromatic diamine may be selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline, 4,4'-ODA), 2,2-bis (4- [4-aminophenoxy] -phenyl) propane, BAPP, , 2'-dimethyl-4,4'-diaminobiphenyl (m-TB-HG), 2,2'-bis (trifluoromethyl) benzidine Bis (3-aminophenoxy) benzene, APBN), 3,5-bis (3-aminophenoxy) benzene, Diaminobenzotrifluoride (DABTF), 1,3-bis (4-aminophenoxy) benzene, TPE-R), 2,2- Bis (4- [3-aminophenoxy] phenyl) sulfone, m-BAPS), 4,4'-diaminobenzanilide (4 , 4'-diaminobenzanilide, DABA), 4,4'-bis (4-aminophenoxy) biphenyl, BAPB, 2,2- 4-aminophenoxyphe (HFBAPP), 4,4'-diaminodiphenylsulfone (DDS), and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane. Bis [4- (4-aminophenoxy) phenyl] sulfone, and BAPS).

The aromatic diamine may essentially contain 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP).

The aromatic diamine may contain 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP).

Wherein the aromatic diamine is at least one selected from the group consisting of 50 to 95 mol% of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP ) 5 to 50 mol%.

The first polyimide precursor solution may further include an inorganic filler.

The inorganic filler may include at least one selected from the group consisting of Talc, Mica, Silica and Calcium Carbonate.

The average particle diameter of the inorganic filler may be 0.1 to 10.0 mu m.

The ten point average roughness Rz of the surface of the metal layer may be 0.5 to 2 탆.

Wherein the metal layer is one or two selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag) May be a thin film of an alloy of more than two kinds.

The thickness of the first polyimide layer may be between 5 and 25 mu m.

The thickness of the second polyimide layer may be 1 to 10 탆.

According to another embodiment of the present invention, there is provided a method of manufacturing a flexible metal laminate, comprising the steps of: preparing two cross-section flexible metal lamination plates in which a first polyimide layer and a second polyimide layer are sequentially arranged on a metal layer; And And a step of laminating the second polyimide layers included in each of the prepared two-sided flexible metal laminates so as to be in contact with each other.

The step of preparing the one-sided flexible metal-

Coating and drying the first polyimide precursor solution on the metal layer; And

Coating the second polyimide precursor solution on the dried first polyimide precursor solution, and then drying and curing the second polyimide precursor solution.

Wherein the first polyimide precursor solution is formed by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine in the presence of a solvent,

At least one of the aromatic tetracarboxylic dianhydride and the compound contained in the aromatic diamine may be substituted with a fluorine atom.

The aromatic tetracarboxylic dianhydride may be selected from the group consisting of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic 4,4'- (4,4'-isopropylidene diphenoxy) -bis- (phthalic dianhydride) (BPADA), 4,4'-diphenylmethane diisocyanate ), Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DCPD-DA), 3,4,3 ', 4'-diphenylsulfone tetracarboxylic (DSDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTTDA) And at least one selected from the group consisting of

The aromatic diamine may be selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline (4,4'- - (4-aminophenoxy) -phenyl) propane (BAPP), 2,2'-dimethyl-4,4'- diaminobiphenyl Methyl) benzidine (TFMB), 1,3'-bis (3-aminophenoxy) benzene (APBN), 3,5-dianobenzotrifluoride (DABTF), 1,3- ) Benzene (TPE-R), 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone (m-BAPS), 4,4'- diaminobenzanilide (4-aminophenoxy) biphenyl (BAPB), 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), 4,4'- (DDS), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS).

The aromatic diamine may essentially contain 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP).

The aromatic diamine may contain 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP).

Wherein the aromatic diamine is at least one selected from the group consisting of 50 to 95 mol% of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP ) 5 to 50 mol%.

The first polyimide precursor solution may further include an inorganic filler.

The solvent may be selected from the group consisting of N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethylsulfoxide Cyclohexane, acetonitrile, and the like.

The solvent may comprise from 70 to 90% by weight, based on the total weight of the first polyimide precursor solution.

The lamination may be performed at 300 to 400 ° C.

The double-sided flexible metal clad laminate provided by the present invention has a low dielectric constant property, and is also excellent in low hygroscopicity, high heat resistance, chemical resistance, dimensional stability, adhesiveness and appearance uniformity.

The method of manufacturing a double-sided flexible metal clad laminate according to the present invention can reduce the number of coatings for forming a polyimide layer, economize on manufacturing process and cost reduction, The curl phenomenon can be prevented, and the workability of the laminated board can be further improved.

FIG. 1 is a conceptual view schematically showing a cross-sectional structure of a double-sided flexible metal-clad laminate according to an embodiment of the present invention.
2 is a schematic view showing a manufacturing process of a conventional double-sided flexible metal clad laminate.
3 is a flow chart schematically illustrating a manufacturing process of a double-sided flexible metal clad laminate according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

More particularly, the present invention relates to a flexible metal clad laminate comprising a polyimide layer having a low dielectric constant and excellent in heat resistance, chemical resistance, dimensional stability, adhesion and appearance uniformity, And a manufacturing method thereof.

Specifically, according to an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: a first polyimide layer including two metal layers opposed to each other; A second polyimide layer; A second polyimide layer; And a first polyimide layer are sequentially arranged on the first polyimide layer.

FIG. 1 is a conceptual view showing a cross-sectional structure of a double-sided flexible metal clad laminate according to an embodiment of the present invention, wherein a first polyimide layer 10, a second polyimide layer 20, 2 polyimide layer 21 and a first polyimide layer 11 are laminated in this order on the first polyimide layer 11 stacked on the uppermost layer.

However, the double-sided flexible metal clad laminate according to the present invention is not limited to the structure shown in FIG. 1, but may further include a polyimide layer as needed in order to reduce the occurrence of curl and increase adhesion to the metal layer. can do. A further included polyimide layer may be located between the metal layer and the first polyimide layer or between the first polyimide layer and the second polyimide layer.

Meanwhile, in the present invention, the metal layer is selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag) One or two or more kinds of alloy thin films can be used, and a copper foil having excellent electric conductivity and low cost can be used.

The thickness of the metal layer is not particularly limited, but may be, for example, 5 to 50 占 퐉.

In addition, the ten point average roughness Rz of the surface of the metal layer may be 0.5 to 2 탆, more preferably 1 to 2 탆. When the ten-point average roughness Rz is less than 0.5 占 퐉, there may be a problem that the adhesive force with the polyimide layer is lowered. When the average roughness Rz is more than 2.5 占 퐉, the surface roughness increases and the transmission loss increases in the high- have.

In the present invention, the first polyimide layer and the second polyimide layer corresponding to the insulating layer are formed by reacting an aromatic tetracarboxylic acid dianhydride with an aromatic diamine in the presence of a solvent, And the second polyimide precursor solution may be the same or different in composition from the first polyimide precursor solution and the second polyimide precursor solution.

The aromatic tetracarboxylic dianhydride may be reacted in an amount of 0.9 to 1.1 equivalents based on 1 equivalent of the aromatic diamine, preferably 0.95 to 1.05 equivalents, more preferably 0.96 to 1.00 equivalents, can do.

In the present invention, examples of the aromatic tetra-carbamic dianhydride include 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2'- (3,4-dicarboxyphenyl) hexafluoropropane, 6FDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2' - bis [(dicarboxyphenoxy) phenyl] propane, BSAA), pyromellitic dianhydride (PMDA), 3,3 ', 4 4,4'-benzotetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-oxydiphthalic dianhydride 4,4 '- (4,4'-isopropylidenediphenoxy) -bis- (phthalic anhydride), BPADA (4,4'- , Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle [2.2.2] oct-7-en-2,3,5,6-tetracarboxylic dianhydride, DCPD-DA), 3,4,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride (DSDA) and 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalen -1,2-dicarboxylic anhydride, DTTDA) can be used.

In the present invention, the aromatic diamine includes, for example, p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA) Oxydianiline, 4,4'-ODA, 2,2-bis (4- [4- (4-aminophenoxy) aminophenoxy] -phenyl) propane, BAPP), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB- Bis (trifluoromethyl) benzidine, TFMB), 1,3'-bis (3-aminophenoxy) benzene, aminophenoxy) benzene, APBN), 3,5-diaminobenzotrifluoride (DABTF), 1,3-bis (4-aminophenoxy) benzene ) benzene, TPE-R), 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, m- , 4'-diaminobenzanilide (DABA), 4,4'-bis (4-aminophenoxy) biphenyl, BAPB), 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane, HFBAPP), 4,4 ' (4,4'-diaminodiphenylsulfone, DDS), bis [4- (4-aminophenoxy) phenyl] sulfone, and BAPS May be used.

However, in the present invention, at least one of the aromatic tetracarboxylic dianhydride and the compound contained in the aromatic diamine used for forming the first polyimide precursor solution is substituted with a fluorine atom, so that the characteristic of the fluorine atom having a low polarity , It is possible to secure a low dielectric constant and a low dielectric loss factor characteristic even when the fluororesin is not additionally contained as in the prior art, and the rigidity of the first polyimide layer can be enhanced and excellent chemical resistance can be ensured.

In the present invention, the first polyimide layer is formed by essentially using 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), optionally substituted with a fluorine atom It is preferably formed using an aromatic diamine containing an aromatic diamine compound. The 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane has a fluorine moiety and can realize a low-dielectric property in a polyimide layer formed therefrom. It is possible to prevent the polyimide layer from becoming stiff due to its flexible nature.

Preferably, the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). If the content of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane is less than 5 mol%, the effect of lowering the dielectric constant may be insignificant. If the content exceeds 50 mol% The moisture absorption and heat resistance is lowered, and the physical properties may be significantly lowered by increasing the CTE.

More preferably, the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) and 2,2'- Methyl) benzidine (TFMB), and most preferably from 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) '-Tris (trifluoromethyl) benzidine (TFMB) in an amount of 50 mol% can be used.

Also, in the present invention, the first polyimide precursor solution and the second polyimide precursor solution used for forming the first polyimide layer and the second polyimide layer may further include an inorganic filler for improving dimensional stability and CTE .

The inorganic filler may include at least one selected from the group consisting of Talc, Mica, Silica, and Calcium Carbonate.

The average particle diameter of the inorganic filler is preferably 0.1 to 10 mu m. When the average particle diameter is less than 0.1 占 퐉, the inorganic filler may have a large surface area and may have poor dispersibility in the polyimide precursor solution. When the average particle diameter exceeds 10 占 퐉, The property may be degraded.

In the present invention, the thickness of the first polyimide layer is not particularly limited, but may be 5 to 25 탆, or 7 to 23 탆, or 10 to 20 탆, in order to secure excellent dielectric properties, mechanical properties, . When the thickness of the first polyimide layer is less than 5 탆, the mechanical properties and dimensional stability of the entire polyimide layer may be impaired. When the thickness exceeds 25 탆, curl occurs in the laminate during the manufacturing process So that it becomes difficult to carry out the curing process thereafter.

In the present invention, the thickness of the second polyimide layer is not particularly limited, but it is preferably 1 to 10 占 퐉 or 2 to 7 占 퐉 in order to ensure low dielectric constant and enable lamination. If the thickness of the second polyimide layer is less than 1 占 퐉, there may be a problem that the adhesion to the metal layer is lowered. If the thickness exceeds 10 占 퐉, the mechanical properties and dimensional stability may be deteriorated.

In the double-sided flexible metal clad laminate according to the present invention, the polyimide layer included between two metal layers opposed to each other has a low dielectric constant at a frequency of 1 GHz of less than 2.0 and less than 3.0, A fluororesin or the like need not be used separately. Therefore, the problem of adhesion deterioration and appearance nonuniformity, which has hitherto been problematic, does not occur, and economical effect due to cost reduction can be achieved.

According to another embodiment of the present invention, there is provided a method of manufacturing a flexible metal laminate, comprising the steps of: preparing two cross-section flexible metal lamination plates in which a first polyimide layer and a second polyimide layer are sequentially arranged on a metal layer; And a step of laminating the first polyimide layer and the second polyimide layer included in the prepared two-sided flexible metal laminates so that they are in contact with each other.

Specifically, in the present invention, the cross-linked flexible metal laminate includes: coating a first polyimide precursor solution on a metal layer and then drying the first polyimide precursor solution; And coating the second polyimide precursor solution on the dried first polyimide precursor solution, followed by drying and curing.

As described above, in the present invention, the polyimide is not directly used for forming the first polyimide layer and the second polyimide layer, but imidized by a process of curing using a polyimide precursor solution to form polyimide Layer can be formed.

Further, in the present invention, prior to the step of coating the first polyimide precursor solution or the step of coating the second polyimide layer as needed to reduce the occurrence of curl and increase the adhesion with the metal layer, And forming a polyimide layer on the intermediate layer. Here, a polyimide layer formed additionally may be formed between the metal layer and the first polyimide layer or between the first polyimide layer and the second polyimide layer.

In the present invention, the first polyimide precursor solution and the second polyimide precursor solution may be used to form the first polyimide layer and the second polyimide layer. These polyimide precursor solutions may be prepared by reacting an aromatic tetracarboxylic dianhydride the first polyimide precursor solution and the second polyimide precursor solution may be the same or different from each other in the reaction between aromatic tetracarboxylic acid dianhydride and aromatic diamine.

The aromatic tetracarboxylic dianhydride may be reacted in an amount of 0.9 to 1.1 equivalents based on 1 equivalent of the aromatic diamine, preferably 0.95 to 1.05 equivalents, more preferably 0.96 to 1.00 equivalents ≪ / RTI >

Examples of the aromatic tetracarboxylic dianhydride in the present invention include 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,3 ' , 3,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), pyromellitic dianhydride (PMDA) 3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA), 4,4' - (4,4'- ) -Bis- (phthalic dianhydride) (BPADA), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DCPD- 3 ', 4'-diphenylsulfone tetracarboxylic anhydride (DSDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- And 2-dicarboxylic anhydride (DTTDA) may be used.

Examples of the aromatic diamine used in the present invention include p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline '-ODA), 2,2-bis (4- [4-aminophenoxy] -phenyl) propane (BAPP), 2,2'-dimethyl-4,4'- diaminobiphenyl ), 3,5-dianobenzotrifluoride (DABTF), 2,2'-bis (trifluoromethyl) benzidine (TFMB), 1,3'- (M-BAPS), 4,4'-bis (4-aminophenoxy) benzene (TPE- (DABA), 4,4'-bis (4-aminophenoxy) biphenyl (BAPB), 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), 4,4'-diaminodiphenylsulfone (DDS) and bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS).

However, in the present invention, at least one of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound is substituted with a fluorine atom during the preparation of the first polyimide precursor solution, The characteristics of low dielectric constant and low dielectric loss factor can be ensured without addition of a fluorine resin as in the prior art, and the rigidity of the first polyimide layer can be enhanced to ensure excellent chemical resistance.

In the present invention, the first polyimide precursor solution is prepared by essentially using 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), optionally substituted with a fluorine atom It is preferable to use an aromatic diamine containing a non-aromatic diamine compound. The 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane has a fluorine moiety and can realize a low-dielectric property in a polyimide layer formed therefrom. It is possible to prevent the polyimide layer from becoming stiff due to its flexible nature.

Preferably, the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). If the content of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane is less than 5 mol%, the effect of lowering the dielectric constant may be insignificant. If the content exceeds 50 mol% The moisture absorption and heat resistance is lowered, and the physical properties may be significantly lowered by increasing the CTE.

More preferably, the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) and 2,2'- Methyl) benzidine (TFMB), and most preferably from 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) '-Tris (trifluoromethyl) benzidine (TFMB) in an amount of 50 mol% can be used.

In the present invention, the type of the solvent used in the preparation of the first polyimide precursor solution and the second polyimide precursor solution is not particularly limited and any organic solvent generally used in the art can be used without limitation, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N, N-dimethylacetamide (DMAc), tetrahydrofuran , Cyclohexane, and acetonitrile can be used.

The amount of the solvent to be used is not particularly limited, but is preferably 70 to 90% by weight based on the total weight of the polyimide precursor solution.

In addition, in the present invention, the first polyimide precursor solution, the second polyimide precursor solution, or both may further contain an inorganic filler in order to improve dimensional stability and CTE as needed.

At this time, the inorganic filler may include at least one selected from the group consisting of Talc, Mica, Silica, and Calcium Carbonate.

The average particle diameter of the inorganic filler is preferably 0.1 to 10 mu m. When the average particle diameter is less than 0.1 占 퐉, the inorganic filler may have a large surface area and may have poor dispersibility in the polyimide precursor solution. When the average particle diameter exceeds 10 占 퐉, The property may be degraded.

In the present invention, the method of coating the first polyimide precursor solution and the second polyimide precursor solution is not particularly limited, but may be a casting method, for example.

Also, the drying may be performed at 100 to 200 ° C, and the curing may be performed at 300 to 400 ° C for 5 to 60 minutes.

When the flexible metal laminate plate is prepared in this invention, it is possible to perform a step of lamination such that the second polyimide layer of the two prepared flexible metal laminate plates contact with each other, and the lamination is performed at a temperature of 300 to 400 ° C . ≪ / RTI >

FIG. 2 is a schematic view showing a manufacturing process of a conventional double-sided flexible metal clad laminate. Referring to FIG. 2, a polyimide layer 30 is formed on a metal layer 1 in multiple layers, And the metal layer 2 is roll laminated on the polyimide layer 40 located at the bottom.

3 is a schematic view showing a manufacturing process of a double-sided flexible metal clad laminate according to an embodiment of the present invention. A heating roll 100 is used to form a first polyimide layer 10 And the second polyimide layers 20 and 21 are laminated by roll lamination of the first and second polyimide layers 11 and 20 and the second polyimide layers 20 and 21, can see.

As described above, according to the manufacturing method of the present invention, unlike the conventional manufacturing process, after preparing two cross-section flexible metal laminate plates, the second polyimide layers disposed on the upper layer of each of the cross-section flexible metal laminate plates are brought into contact with each other, The laminate is laminated so that the front surface of the metal layer on both sides of the first polyimide layer is disposed on the outer side of the laminate so as to reduce the number of times of coating so as to prevent curl which may occur in the laminate after coating, , Cost savings and streamlining of the manufacturing process can be economically beneficial.

Example

Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example 1] Preparation of second polyimide precursor solution

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 14.91 g (0.036 mol) of 2,2-bis (Aminophenoxy) -phenyl) propane (BAPP) and 10.62 g (0.036 mol) of 1,3'-bis (3-aminophenoxy) benzene (APBN) were added and stirred at 50 ° C to dissolve completely. To this solution, 10.69 g (0.036 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2,2'-bis [(dicarboxyphenoxy) 18.91 g (0.036 mol) of water (BSAA) was slowly added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 15,000 cps.

[Synthesis Example 2] Preparation of first polyimide precursor solution (1)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet, and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 10.78 g (0.034 mol) of 2,2'- Bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) was added to the solution and stirred at 50 DEG C to dissolve the solution completely . To this solution were added 23.94 g (0.054 mol) of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropanedioanhydride (6FDA) and 2.94 g (0.013 mol) of pyromellitic dianhydride (PMDA) was slowly added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 35,000 cps.

[Synthesis Example 3] Preparation of first polyimide precursor solution (2)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 11.76 g (0.037 mol) of 2,2'- Bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) was added and stirred at 50 DEG C to dissolve completely . To this solution was added 16.31 g (0.037 mol) of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropanedioanhydride (6FDA) and 8.01 g (0.037 mol) of pyromellitic dianhydride (PMDA) was gradually added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 33,000 cps.

[Synthesis Example 4] Preparation of first polyimide precursor solution (3)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 13.84 g (0.043 mol) of 2,2'- Bis (4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) was added to the solution and stirred at 50 ° C to dissolve completely . 18.86 g (0.086 mol) of pyromellitic dianhydride (PMDA) was slowly added to this solution and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 28,000 cps.

[Synthesis Example 5] Preparation of first polyimide precursor solution (4)

2.76 g of Talc was added to NMP and stirred, followed by addition of TFMB, HFBAPP, 6FDA and PMDA in succession to obtain a polyamic acid solution having a viscosity of 30,000 cps.

[Synthesis Example 6] Preparation of first polyimide precursor solution (5)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 4.02 g (0.013 mol) of 2,2'- Bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) (26.04 g, 0.05 mol) was added to the flask and stirred at 50 ° C to dissolve . To this solution, 22.32 g (0.05 mol) of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate (6FDA) and 2.74 g (0.013 mol) of pyromellitic dianhydride (PMDA) was slowly added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 38,000 cps.

[Synthesis Example 7] Preparation of first polyimide precursor solution (6)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet, and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 4.36 g (0.014 mol) of 2,2'- Bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP) (28.22 g, 0.054 mol) . To this solution was added 15.12 g (0.034 mol) of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropanedioanhydride (6FDA) and 7.42 g (0.034 mol) of pyromellitic dianhydride (PMDA) was slowly added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 35.000 cps.

[Synthesis Example 8] Preparation of first polyimide precursor solution (7)

11.02 g of polytetrafluoroethylene (PTFE) filler was added to NMP and stirred, followed by addition of TFMB, HFBAPP, 6FDA and PMDA in succession to obtain a polyamic acid solution having a viscosity of 28,000 cps. .

[Synthesis Example 9] Preparation of first polyimide precursor solution (8)

27.56 g of polytetrafluoroethylene (PTFE) filler was added to NMP and stirred, followed by the addition of TFMB, HFBAPP, 6FDA and PMDA in succession to a polyamic acid solution having a viscosity of 24,000 cps ≪ / RTI >

[Synthesis Example 10] Preparation of first polyimide precursor solution (9)

In a four-neck reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a powder dispensing funnel, 220 g of N-methylpyrrolidone (NMP) and 12.31 g (0.061 mol) of 4,4'-oxydianiline ODA) and 6.65 g (0.061 mol) of phenylenediamine (PDA) were added and stirred at 50 ° C to dissolve completely. 36.17 g (0.123 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was slowly added to this solution and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 45,000 cps. .

[Synthesis Example 11] Preparation of the first polyimide precursor solution (10)

220 g of N-methylpyrrolidone (NMP) and 14.81 g (0.137 mol) of phenylenediamine (PDA) were added to a four-necked reaction vessel equipped with a thermometer, a stirrer and a nitrogen inlet and a powder dispensing funnel, RTI ID = 0.0 > C < / RTI > To this solution, 40.31 g (0.137 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was slowly added and polymerization was carried out with stirring for 10 hours to obtain a polyamic acid solution having a viscosity of 40,000 cps. .

[Synthesis Example 12] Preparation of the first polyimide precursor solution (11)

2.76 g of talc was added to NMP and stirred, followed by the addition of ODA, PDA and BPDA in succession to obtain a polyamic acid solution having a viscosity of 39,000 cps.

 [Examples 1 to 4]

The copper foil was coated with the first polyimide precursor solution prepared in Synthesis Examples 2 to 5 and then dried at 175 캜 for 2 minutes. To the dried first polyimide precursor solution, the second polyimide precursor solution prepared in Synthesis Example 1 Coated and then dried at 190 캜 for 2.5 minutes. Thereafter, it was heated in a nitrogen oven at room temperature and cured at 350 ° C for 30 minutes to prepare a flexible metal laminate. Two flexible metal laminated plates thus prepared were prepared, and then the second polyimide layers were brought into contact with each other. Then, the laminated plates were bonded at 380 ° C using a laminator to produce a double-sided flexible metal laminate.

[Comparative Examples 1 to 7]

The double-sided flexible metal clad laminate was produced using the same process as in the above example, but using the one prepared in Synthesis Examples 6 to 12 as the first polyimide precursor solution.

[Experimental Example 1]

The dielectric constant, CTE, moisture absorption and heat resistance and peel strength of the double-sided flexible metal clad laminate produced according to Examples 1 to 4 and Comparative Examples 1 to 7 were measured according to the following methods, Respectively.

(1) Permittivity

The double-sided flexible metal laminate was measured using a material analyzer according to the test standard of IPC TM-650.2.5.5.1.

(2) CTE measurement

The dimensional change was measured at a temperature range of 100 to 200 ° C using a TMA instrument.

(3) Measurement of moisture absorption resistance

The laminate cut into a size of 5 x 5 cm was put in a chamber of 85 ° C and 85% humidity for 24 hours, and then placed on a 288 ° C water bath, and visual changes were observed for 10 minutes.

(4) Adhesiveness

Measured according to the test standard of IPC-TM-650.2.4.8.

division permittivity
(Dk) CTE
(ppm) Moisture absorption heat resistance
(288 DEG C) Adhesiveness
(Kgf / cm) Example 1 2.7 35 > 320 1.2 Example 2 2.7 30 > 320 1.1 Example 3 2.9 28 > 320 One Example 4 2.8 25 320 One Comparative Example 1 2.7 42 280 1.4 Comparative Example 2 2.7 38 280 1.3 Comparative Example 3 2.6 33 290 0.6 Comparative Example 4 2.5 35 280 0.4 Comparative Example 5 3.2 25 > 350 1.2 Comparative Example 6 3.4 18 > 350 > 1.5 Comparative Example 7 3.3 20 350 1.1

As shown in Table 1, the double-sided flexible metal clad laminate produced in Examples 1 to 4 belonging to the scope of the present invention has a dielectric constant (Dk) of less than 3.0, but the aromatic diamine not substituted with fluorine atoms and the aromatic tetracarboxylic acid It can be seen that the dielectric constant of the double-sided flexible metal clad laminate of Comparative Examples 5 to 7, in which the first polyimide layer was formed using the phoxylic dianhydride, exceeded 3.0.

In addition, the double-sided flexible metal laminate sheets of Examples 1 to 4 exhibited excellent CTE, hygroscopic heat resistance and adhesiveness, but Comparative Example 3 using Teflon filler in addition to the first polyimide precursor solution and 4, the dielectric constant Dk has a value of less than 3.0, but has a very low adhesive force of 0.6 Kgf / cm and 0.4 Kgf / cm, respectively, and has a very low moisture absorption and heat resistance.

Further, in the case of the first polyimide precursor solution, in Comparative Examples 1 and 2 in which HFBAPP in an amount of more than 50 mol% in the aromatic diamine was used, the hygroscopic heat resistance was lowered and the CTE value It is possible to easily predict that the physical properties are remarkably deteriorated.

As a result, the double-sided flexible metal clad laminate within the scope of the present invention can exhibit low hygroscopicity, high heat resistance, chemical resistance, dimensional stability, adhesion and appearance uniformity, while securing the characteristics of low dielectric constant.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.

1, 2: metal layer
10, 11: a first polyimide layer
20, 21: a second polyimide layer
30, 40: polyimide layer
100: heating roll

Claims (26)

And two metal layers opposed to each other,
A first polyimide layer between the two metal layers; A second polyimide layer; A second polyimide layer; And the first polyimide layer are sequentially arranged. The method according to claim 1,
The first polyimide layer is obtained by imidizing a first polyimide precursor solution obtained by reacting an aromatic tetracarboxylic acid dianhydride and an aromatic diamine in the presence of a solvent,
Wherein at least one of the aromatic tetracarboxylic dianhydride and the compound contained in the aromatic diamine is substituted with a fluorine atom. 3. The method of claim 2,
The aromatic tetracarboxylic dianhydride may be selected from the group consisting of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane (6FDA), 2,2'- 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis [(dicarboxyphenoxy) phenyl] propane (Dicarboxyphenoxy) phenyl] propane, BSAA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ', 4,4'-benzotetracarboxylic dianhydride, BTDA), 4,4'-oxydiphthalic dianhydride (ODPA), 4,4' - (4,4'-iso (4,4 '- (4,4'-isopropylidenediphenoxy) -bis- (phthalic anhydride), BPADA), bicyclo [2.2.2] oct- -Ene-2,3,5,6-tetracarboxylic dianhydride (DCPD-DA), 3,4,3-tetracarboxylic dianhydride (bicycle [2.2.2] oct- ', 4'-diphenylsulfone tetracarboxylic (3,4,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, DSDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene 1,2-dicarboxylic anhydride (DTTDA), which is selected from the group consisting of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalen-1,2-dicarboxylic anhydride A double-sided flexible metal laminate comprising at least one member. 3. The method of claim 2,
The aromatic diamine may be selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline, 4,4'-ODA), 2,2-bis (4- [4-aminophenoxy] -phenyl) propane, BAPP, , 2'-dimethyl-4,4'-diaminobiphenyl (m-TB-HG), 2,2'-bis (trifluoromethyl) benzidine Bis (3-aminophenoxy) benzene, APBN), 3,5-bis (3-aminophenoxy) benzene, Diaminobenzotrifluoride (DABTF), 1,3-bis (4-aminophenoxy) benzene, TPE-R), 2,2- Bis (4- [3-aminophenoxy] phenyl) sulfone, m-BAPS), 4,4'-diaminobenzanilide (4 , 4'-diaminobenzanilide, DABA), 4,4'-bis (4-aminophenoxy) biphenyl, BAPB, 2,2- 4-aminophenoxyphe (HFBAPP), 4,4'-diaminodiphenylsulfone (DDS), and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane. And at least one selected from the group consisting of bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone and BAPS. 5. The method of claim 4,
Wherein the aromatic diamine essentially comprises 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). 6. The method of claim 5,
Wherein the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). The method according to claim 6,
Wherein the aromatic diamine is at least one selected from the group consisting of 50 to 95 mol% of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP ) 5 to 50 mol%. 3. The method of claim 2,
Wherein the first polyimide precursor solution further comprises an inorganic filler. 9. The method of claim 8,
Wherein the inorganic filler comprises at least one selected from the group consisting of Talc, Mica, Silica and Calcium Carbonate. 9. The method of claim 8,
Wherein the inorganic filler has an average particle diameter of 0.1 to 10.0 占 퐉. The method according to claim 1,
And a ten-point average roughness (Rz) of the surface of the metal layer is 0.5 to 2 占 퐉. The method according to claim 1,
Wherein the metal layer is one or two selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag) Sided flexible metal clad laminate. The method according to claim 1,
Wherein the thickness of the first polyimide layer is 5 to 25 占 퐉. The method according to claim 1,
Wherein the thickness of the second polyimide layer is 1 to 10 占 퐉. Preparing two cross-section flexible metal laminates on which a first polyimide layer and a second polyimide layer are sequentially arranged on a metal layer; And
And laminating the second polyimide layers included in each of the prepared two-sided flexible metal laminates so as to be in contact with each other. 16. The method of claim 15,
The step of preparing the one-sided flexible metal-
Coating and drying the first polyimide precursor solution on the metal layer; And
Coating the second polyimide precursor solution on the dried first polyimide precursor solution, and then drying and curing the second polyimide precursor solution. 17. The method of claim 16,
Wherein the first polyimide precursor solution is formed by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine in the presence of a solvent,
Wherein at least one of the aromatic tetracarboxylic dianhydride and the compound contained in the aromatic diamine is substituted with a fluorine atom. 18. The method of claim 17,
The aromatic tetracarboxylic dianhydride may be selected from the group consisting of 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic 4,4'- (4,4'-isopropylidene diphenoxy) -bis- (phthalic dianhydride) (BPADA), 4,4'-diphenylmethane diisocyanate ), Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DCPD-DA), 3,4,3 ', 4'-diphenylsulfone tetracarboxylic (DSDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTTDA) Sided flexible metal clad laminate according to any one of claims 1 to 3. 18. The method of claim 17,
The aromatic diamine may be selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline (4,4'- - (4-aminophenoxy) -phenyl) propane (BAPP), 2,2'-dimethyl-4,4'- diaminobiphenyl Methyl) benzidine (TFMB), 1,3'-bis (3-aminophenoxy) benzene (APBN), 3,5-dianobenzotrifluoride (DABTF), 1,3- ) Benzene (TPE-R), 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone (m-BAPS), 4,4'- diaminobenzanilide (4-aminophenoxy) biphenyl (BAPB), 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), 4,4'- (DDS), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS). 20. The method of claim 19,
Wherein the aromatic diamine essentially comprises 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). 21. The method of claim 20,
Wherein the aromatic diamine comprises 5 to 50 mol% of 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP). 22. The method of claim 21,
Wherein the aromatic diamine is at least one selected from the group consisting of 50 to 95 mol% of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP ) Of 5 to 50 mol%. 18. The method of claim 17,
Wherein the first polyimide precursor solution further comprises an inorganic filler. 18. The method of claim 17,
The solvent may be selected from the group consisting of N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethylsulfoxide And at least one selected from the group consisting of cyclohexane and acetonitrile. 18. The method of claim 17,
Wherein the solvent is contained in an amount of 70 to 90% by weight based on the total weight of the first polyimide precursor solution. 16. The method of claim 15,
Wherein the lamination is performed at 300 to 400 캜.

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