TWI688314B - Resin-coated metal foil for manufacturing of printed circuit board, printed circuit board, and method of manufacturing the same - Google Patents

Abstract

A resin-coated metal foil for the manufacturing of a printed circuit board, a printed circuit board, and a method of manufacturing the same are provided.  The resin-coated metal foil for manufacturing a printed circuit board includes a resin layer formed on a surface of a metal foil, and the resin layer contains a naphthalene-based epoxy resin, an epoxy resin curing agent, and a polyimide or polyamideimide resin dissolved in a solvent having a boiling point of 150°C or less.

Description

Resin-coated metal foil for manufacturing printed circuit boards, printed circuit boards, and methods for manufacturing the above

This application claims the priority and rights of Korean Patent Application No. 10-2014-0086681 filed on July 10, 2014 at the Korea Intellectual Property Office. The disclosure content of the Korean patent application is incorporated into this case for reference .

The invention relates to a resin-coated metal foil for manufacturing a printed circuit board, a printed circuit board, and a method for manufacturing the above.

A printed circuit board is manufactured by forming a circuit pattern on an insulating material using a conductive material such as copper. In accordance with the miniaturization and portability of electronic components, fine circuit patterns with higher density are required.

[Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-070176

One aspect of the present invention can provide a resin-coated metal foil for manufacturing a printed circuit board, and a fine circuit pattern can be easily processed by plating a resin layer on the metal foil, the resin layer and the metal plating layer forming the circuit pattern Has excellent tight adhesion characteristics and high heat resistance.

An aspect of the present invention may also provide a printed circuit board manufactured using the resin-plated metal foil for manufacturing the printed circuit board, and a method of manufacturing the printed circuit board.

According to one aspect of the present invention, the resin-coated metal foil for manufacturing a printed circuit board may include a resin layer formed on the surface of the metal foil. The resin layer may contain a naphthalene-based epoxy resin; an epoxy resin curing agent; and a polyimide resin or a polyamide imide resin soluble in a solvent having a boiling point of 150°C or lower.

According to another aspect of the present invention, a method of manufacturing a printed circuit board may include: stacking the resin-plated metal foil as described above on an insulating layer; removing the metal foil of the resin-plated metal foil; and the metal A circuit pattern is formed on the resin layer of the resin-coated metal foil from which the foil has been removed.

According to another aspect of the present invention, the printed circuit may include a resin layer formed on the printed circuit, wherein the resin layer contains a naphthalene-based epoxy resin; an epoxy resin curing agent; and a soluble boiling point of 150°C Or polyimide resin or polyamide imide resin in a solvent below 150°C.

10: Metal foil

20: resin layer

100: resin-coated metal foil

Reading the following detailed description in conjunction with the accompanying drawings will more clearly understand the above and other aspects, features, and other advantages of the present invention. In the drawings: FIG. 1 is a plating resin for manufacturing a printed circuit board according to an exemplary embodiment of the present invention Sectional view of metal foil.

Exemplary embodiments of the present invention will now be explained in detail with reference to the drawings.

However, the present invention can be exemplified in many different forms and should not be considered as limited to the specific embodiments described herein. Rather, the embodiments are provided to make the disclosure of the present invention thorough and complete, and fully convey the scope of the present invention to those skilled in the art.

In the drawings, the shape and size of each element may be exaggerated for clarity, and the same reference numbers will be used throughout the text to refer to the same or similar elements.

1 is a cross-sectional view of a resin-coated metal foil for manufacturing a printed circuit board according to an exemplary embodiment of the present invention.

Referring to FIG. 1, in a resin-plated metal foil 100 according to an exemplary embodiment of the present invention, a resin layer 20 may be formed on one surface of the metal foil 10.

The resin layer 20 may contain a naphthalene-based epoxy resin, an epoxy resin curing agent, and a polyimide resin or a polyamideimide resin soluble in a solvent having a boiling point of 150°C or lower .

The naphthalene-based epoxy resin may be a naphthalene-based epoxy resin in a liquid phase at room temperature, for example, at a temperature of 20±5° C., and has an equivalent weight of 160 or less.

In the case where the equivalent weight of the naphthalene-based epoxy resin is greater than 160, the resin layer 20 may not be uniformly formed, resulting in deterioration of solder heat resistance.

The epoxy resin curing agent may include one or more selected from the group consisting of: phenol-aralkyl type resin (phenol-aralkyl type resin), naphthol-aralkyl type resin (naphthol-aralkyl type resin ), phenyl-type novolac resin, nitrogen-containing novolac resin, dicyclopentadiene-type phenol resin, biphenyl-type phenol resin ) And triphenyl-type phenol resin.

The content of the epoxy resin curing agent derived from the reaction equivalent of the curing resin may not require a specific amount limitation, but the amount of the epoxy resin curing agent contained may be sufficient to sufficiently cure the naphthalene-based epoxy resin.

Polyimide resin or polyimide amide imide resin soluble in a solvent having a boiling point of 150°C or lower can be prepared by reacting a large aromatic diamine (bulky aromatic diamine) with an acid anhydride.

Examples of the aromatic diamine used are not particularly limited, but may include 1,3-bis(4-aminophenoxy)benzene (1,3-bis(4-aminophenoxy)benzene), 1,3-bis (4-Aminophenoxy) biphenyl, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy Group) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] benzene, Bis[4-(3-aminophenoxy)phenyl] ash, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether, 1,4-bis(4 -Aminophenoxy)-2,3,5-trimethylbenzene, 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, 1,4-bis [4-Amino-2-(trifluoromethyl)phenoxy]benzene, 2,2-bis[4-[4-amino-2-(trifluoromethyl)phenyl]hexafluoropropane], 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,3-bis(4-aminophenoxy) neopentane, 2,5-bis(4-aminophenoxy)-biphenyl, 1,3-bis(4-aminophenoxy) -5-(2-phenylethynyl)benzene, 1,3-bis(3-aminophenoxy)-5-(2-phenylethynyl)benzene and 2,4-diamino-4' -Phenylethynyl diphenyl ether (these are based on ethers), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,7-diamino-2,8 -Dimethyldibenzothiophene-5,5-dioxide, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminobenzylamide) Group)-3,3'-dihydroxybiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(4-aminophenyl) stilbene, 4,4 '-Diaminodiphenyl ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, bis{4-(4- Aminophenoxy)phenyl} ketone, 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane and 2,2-bis{4-(4-aminophenoxy Group) phenyl}propane (these are based on biphenyl), 4,4'-diaminodiphenyl sulfone, bis{4-(4-aminophenoxy)phenyl} benzene, bis{4-( 3-aminophenoxy)phenyl} 碸 and 3,7-diamino-2,8-dimethyldibenzothiophene-5,5-dioxide (these are based on 碸) and so on.

Examples of the acid anhydride may include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 3,4, 3',4'-diphenylbenzene tetracarboxylic dianhydride, 3,3'4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,4-tetrahydrofuran tetracarboxylic acetic dianhydride (2, 3,4-tetrahydro furan tetra-carboxylic acid acetic acid dianhydride), 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'- Tetracarboxylic dianhydride (m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride), p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 4,4-oxygen 4,4-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3 or 3,4-dicarboxyphenoxy Group) phenylpropane dianhydride, 2,2-bis[4-(2,3 or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,1,1,3,3,3- Hexafluoro-2,2-bis[4-(2,3 or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride and so on.

In the case of a polyimide resin or a polyimide amide imide resin that is soluble in a solvent having a boiling point higher than 150°C, a relatively large amount of solvent may remain due to the use of a high-boiling point solvent having a boiling point higher than 150°C, When manufacturing a printed circuit board, it may cause a close adhesion with a chemical copper plating layer (chemical copper plating layer) to deteriorate.

In this case, examples of the solvent having a boiling point of 150°C or lower may include methyl ethyl ketone, dimethylformamide, and the like.

Assuming that the sum of the weights of the naphthalene-based epoxy resin and the epoxy resin curing agent is 100 parts by weight, the content of the polyimide resin or the polyamidimide resin can be 5 to 50 parts by weight.

In the case where the content of the polyimide resin or polyimide amide imine resin is less than 5 parts by weight, the adhesive properties may be deteriorated, and in the case where the content is more than 50 parts by weight, the formability may be It may deteriorate, and the resin layer may be unevenly formed.

The resin-coated metal foil 100 can be manufactured as follows: a solvent is added to contain a naphthalene-based epoxy resin, an epoxy resin curing agent, and a soluble boiling point of 150°C or lower A resin varnish is prepared from a resin composition of polyimide resin or polyimide amide imide resin in a solvent at 150° C., and the resin varnish is applied to the roughened surface of the metal foil 10 Instead, the resin layer 20 is formed.

The method of applying the resin varnish to the metal foil 10 is not particularly limited, and can be used by using a roll coater, a knife coater, or a doctor coater blade coater, gravure coater, die coater, multi-die coater, reverse coater, reverse roll coater (reverse roll coater) etc. to adjust the viscosity of the resin varnish to form a resin layer 20 on the surface of the metal foil 10.

As the metal foil 10, a metal foil formed of gold, silver, copper, aluminum, nickel, or an alloy of one or more thereof can be used.

The average surface roughness Ra of the metal foil 10 may be 0.05 μm to 0.2 μm, and the thickness thereof may be 0.1 μm to 5 μm.

The resin layer 20 having a thickness of 0.5 μm to 10 μm may be formed on the surface of the metal foil 10, and the degree of curing of the resin layer 20 may be 70% or higher.

In the case where the degree of curing of the resin layer 20 is less than 70%, when the resin-plated metal foil 100 is pressed-stacked on the insulating layer on which the circuit pattern is to be formed, the resin layer 20 may be blended with the insulating layer Together, this can result in reduced adhesion to the electroless copper plating layer, and solder heat resistance may also be reduced when manufacturing printed circuit boards.

On a printed circuit board manufactured using resin-coated metal foil 100, a naphthalene-based epoxy resin, an epoxy resin curing agent, and a soluble boiling point of 150°C or lower can be formed A resin layer of polyimide resin or polyimide amide imide resin in a solvent at 150°C.

When a resin-coated metal foil 100 is used to manufacture a printed circuit board, a fine circuit pattern can be easily processed, and at the same time, peel strength and solder heat resistance can be ensured.

Next, a method of manufacturing a printed circuit board with fine circuit patterns using the resin-plated metal foil 100 will be explained.

First, the resin-plated metal foil 100 may be stacked so that the resin layer 20 of the resin-plated metal foil 100 is in contact with the surface of the insulating layer on which the circuit pattern is to be formed. After stacking, the metal foil 10 can be removed by etching, and a circuit pattern can be formed on the remaining resin layer 20.

The method of forming the circuit pattern is not particularly limited, but as an example, the circuit pattern can be formed by forming an electroless copper layer on the resin layer 20, forming a patterning plating layer (plating resist), and performing an electroplating process, and The electroless copper plating layer is removed by etching.

As described above, when the resin layer 20 is formed on the insulating layer on which the circuit pattern is to be formed using the resin-plated metal foil 100 to form the circuit pattern, by forming a relatively low surface roughness while also ensuring peel strength and solder heat resistance, Fine circuit patterns can be easily implemented and over-etching can be prevented.

However, the method of manufacturing the printed circuit board using the resin-plated metal foil 100 is not limited to this, but all manufacturing methods known in the art may be used.

In the following, the present invention will be explained in detail by the following examples. However, the following examples do not limit the scope of the present invention, and the purpose of providing the following examples is to help understand the present invention.

<Example 1>

Preparation of 7.2 parts by weight of naphthalene-based epoxy resin (SE-80, Shin-A T&C), 10.2 parts by weight of phenol aralkyl type curing agent (MEHC-7851S, Meiwa Kasei), 7.5 parts by weight A varnish composed of polyamidimide (soluble in a solvent having a boiling point of 150°C or lower) (SORX-S (NKK)) and 0.6 parts by weight of an imidazole curing accelerator.

<Example 2>

Preparation of 5.2 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 2.3 parts by weight of bisphenol A epoxy resin (YD-128K, Kukdo Chemical), 9.9 parts by weight Phenol aralkyl type curing agent (MEHC-7851S, Minghe Chemical), 7.5 parts by weight of polyamidoamide imide (soluble in solvents with a boiling point of 150°C or lower) (SORX-S (NKK )) and 0.6 parts by weight of varnish consisting of imidazole curing accelerator.

<Example 3>

Preparation of 8.7 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 8.8 parts by weight of amino-triazine novolac curing agent (PS6313, Gun Ei Chem. Industry) Co. Ltd.)), 7.5 parts by weight of polyamidimide (soluble in a solvent with a boiling point of 150°C or lower) (SORX-S (NKK)) and 0.2 parts by weight of imidazole curing acceleration Varnish made up of chemicals.

<Example 4>

Preparation of 7.1 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 1.8 parts by weight of bisphenol A epoxy resin (YD-128K, Guodu Chemical) 8.6 parts by weight of amino-triazine novolak curing agent (PS6313, Qunrong Chemical Co., Ltd.), 7.5 parts by weight of polyamidoamide imide (soluble in solvents with a boiling point of 150°C or lower ) (SORX-S (NKK)) and 0.2 parts by weight of varnish composed of imidazole curing accelerator.

<Example 5>

Preparation of 7.2 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 10.2 parts by weight of phenol aralkyl type curing agent (MEHC-7851S, Minghe Chemical), 12.2 parts by weight of polyamidoamide A varnish composed of imine (soluble in a solvent with a boiling point of 150°C or lower) (SORX-S (NKK)) and 0.6 parts by weight of imidazole curing accelerator.

<Example 6>

Preparation of epoxy resin (Polydis3615, Schill+Seilacher) modified from 5.6 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 2.4 parts by weight of nitrile-butadiene rubber (NBR) Struktol" Co., Ltd.), 9.5 parts by weight of phenol aralkyl type curing agent (MEHC-7851S, Meiwa Chemicals), 7.5 parts by weight of polyamidoamide imide (soluble at a boiling point of 150°C or lower Varnish composed of (SORX-S (NKK)) and 0.6 parts by weight of imidazole curing accelerator.

<Example 7>

Preparation of epoxy resin (Polydis3615, Schill+Seilacher "Struktol" Co., Ltd.) modified from 7.3 parts by weight of naphthalene-based epoxy resin (SE-80, Shin-A T&C), 1.8 parts by weight of nitrile rubber (NBR) ), 8.3 heavy A large amount of amine-triazine novolac curing agent (PS6313, Qunrong Chemical Co., Ltd.), 7.5 parts by weight of polyamidimide (soluble in solvents with a boiling point of 150°C or lower) (SORX-S (NKK)) and 0.2 parts by weight of varnish consisting of imidazole curing accelerator.

<Example 8>

Preparation of 7.2 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 1.8 parts by weight of cresol novolac epoxy resin (YDCN-500-8P, Guodu Chemical), 8.5 parts by weight of Amino-triazine novolac curing agent (PS6313, Qunrong Chemical Co., Ltd.), 7.5 parts by weight of polyamidoamide imide (soluble in solvents with a boiling point of 150°C or lower) (SORX- S(NKK)) and 0.2 parts by weight of imidazole curing accelerator.

<Comparative Example 1>

Preparation of 7.2 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 10.2 parts by weight of phenol aralkyl type curing agent (MEHC-7851S, Minghe Chemical), 7.5 parts by weight of polyamidoamide A varnish composed of imine (soluble in a solvent with a boiling point higher than 150°C) (SORX-OB (NKK)) and 0.6 parts by weight of imidazole curing accelerator.

<Comparative Example 2>

28 parts by weight of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane and 19 parts by weight of trimellitic anhydride were dissolved in 260 parts by weight of N-methylpyrrolidone, and Heat at 80°C. Thereafter, toluene was added thereto and refluxed for 3 hours, and the generated moisture was removed. Then, the mixture was kept at 190°C for 2 hours and cooled to room temperature, To this was added 25 parts by weight of 4,4′-diphenylmethane diisocyanate, heated at 170° C. for 2 hours, and cooled to room temperature, thereby synthesizing aromatic polyamidoamide imine (PAI). The average molecular weight Mw of the synthetic polyamidoamide imine was 120,000.

Preparation of 7.5 parts by weight of synthetic polyamidoamide imine, 7.2 parts by weight of naphthalene epoxy resin (SE-80, Shin-A T&C), 10.2 parts by weight of phenol aralkyl type curing agent (MEHC-7851S , Minghe Chemicals) and 0.6 parts by weight of varnish consisting of imidazole curing accelerator.

<Plating Example 1>

Using a pattern coater, the varnishes of Examples 1 to 8 and Comparative Examples 1 and 2 were plated on electrolytic copper foil (MT-EX, Mitsui Metal) with a thickness of 20 μm and a width of 600 mm, respectively. )) on the surface-treated surface so as to have a thickness of 3 microns after removing the solvent. The plated copper foil was passed through four floating-type drying furnaces set to 80°C, 110°C, 170°C, and 170°C and having a length of 2 meters at a rate of 2 meters/minute. The degree of curing of the obtained resin-plated copper foil is 90% or higher.

<Plating Example 2>

The varnish of Example 1 was plated on the surface-treated surface of an electrolytic copper foil (MT-EX, Mitsui Metal) with a thickness of 20 microns and a width of 600 mm using a pattern coater to facilitate removal of the solvent. 3 micron thickness. The plated copper foil was passed through four floating drying furnaces set to 80°C, 110°C, 150°C, and 150°C and having a length of 2 meters at a rate of 2 meters/minute to withstand floating drying. The degree of curing of the obtained resin-plated copper foil was 45%.

In the case of implementing plating example 2, the degree of curing is relatively low (45%), so when laminated, the resin layer of the resin-coated copper foil is blended with polypropylene glycol (PPG) resin, resulting in The tight adhesion of electroless copper plating is reduced, and the solder heat resistance is deteriorated.

<Experimental example>

A resin-coated copper foil sample and a copper-clad laminate (CCL) obtained by plating the varnishes of Examples 1 to 8 and Comparative Examples 1 and 2 according to Plating Example 1 ) And PPG are stacked together at 210°C and a load of 3 million Pascals (MPa) for 130 minutes. After stacking, the copper foil was etched and plated with chemical copper (1 micron) and electrolytic copper (20 microns). Table 1 illustrates the tight adhesion of the copper (Cu)-resin layer obtained from the above example (90° peel strength between the copper (Cu)-resin layer is measured using a universal testing machine (UTM) ; P/S) and solder heat resistance (measurement and observation of the sample can withstand without foaming time in a solder bath at 300 ℃, up to 5 minutes; T-300).

Referring to Table 1, Examples 1 to 4 show excellent close adhesion and solder heat resistance.

On the contrary, in Comparative Example 1, since polyimide amide imide soluble in a solvent having a boiling point higher than 150° C. was used, the plating performance was poor, and due to the large amount of remaining solvent, it was Deterioration of tight adhesion. In addition, in Comparative Example 2, although polyimide amide imide soluble in a solvent having a boiling point higher than 150° C. is used, since the epoxy resin and the curing agent are not uniformly mixed with each other, a varnish cannot be formed.

On the other hand, in Example 5, polyimide amide imide, which is soluble in a solvent having a boiling point of 150° C. or lower, is used, and therefore has excellent close adhesion and solder heat resistance. However, since the content of polyamidimide is too high, the formability is deteriorated, and the appearance of unevenness due to the increased viscosity of the varnish.

In Examples 6 to 8, although polyimide amide imide soluble in a solvent having a boiling point of 150°C or lower was used, the resin was not uniformly formed because the equivalent weight of the epoxy resin was more than 200 Layer, causing the solder heat resistance to deteriorate.

As described above, according to exemplary embodiments of the present invention, by providing a resin layer having excellent adhesion characteristics with the metal plating layer forming the circuit pattern to integrate the resin layer and the metal plating layer with each other, peel strength and solder can be ensured Heat resistant and available The fine circuit pattern is easily processed.

Although exemplary embodiments have been shown and described above, those skilled in the art will understand that modifications and changes can be made without departing from the scope of the invention as defined by the scope of the accompanying patent application.

10‧‧‧Metal foil

20‧‧‧Resin layer

100‧‧‧ Resin-coated metal foil

Claims (7)

A resin-coated metal foil for manufacturing a printed circuit board, the resin-coated metal foil comprising a resin layer formed on the surface of the metal foil, wherein the resin layer contains: a naphthalene-based epoxy resin; an epoxy resin curing agent; and Polyimide resin or polyimide amide imide resin, which is soluble in a solvent having a boiling point of 150°C or lower, and wherein the naphthalene-based epoxy resin has an equivalent weight of 160 or less, wherein When the sum of the weights of the naphthalene-based epoxy resin and the epoxy resin curing agent is 100 parts by weight, the content of the polyimide resin or the polyamide imide resin is 5 parts by weight to 50 parts by weight, and wherein the resin layer has a curing degree of 70% or higher. The resin-coated metal foil for manufacturing a printed circuit board as described in item 1 of the patent application range, wherein the naphthalene-based epoxy resin is in a liquid phase at 20±5°C. The resin-coated metal foil for manufacturing a printed circuit board as described in item 1 of the patent application range, wherein the epoxy resin curing agent is one or more selected from the group consisting of: phenol aralkyl type resin , Naphthol aralkyl resin, phenyl novolak resin, nitrogen-containing novolak resin, dicyclopentadiene phenol resin, biphenyl phenol resin and triphenyl phenol resin. The resin-coated metal foil for manufacturing a printed circuit board as described in item 1 of the patent application range, wherein the resin layer has a thickness of 0.5 to 10 microns. The resin-coated metal foil for manufacturing a printed circuit board as described in item 1 of the patent application range, wherein the metal foil has an average surface roughness Ra of 0.05 μm to 0.2 μm. A method for manufacturing a printed circuit board, comprising: stacking a resin-plated metal foil as described in any one of the patent application items 1 to 5 on an insulating layer; removing the resin-plated metal foil metal foil; And forming a circuit pattern on the resin layer of the resin-plated metal foil from which the metal foil has been removed. A printed circuit board includes a resin layer formed on the printed circuit board, wherein the resin layer contains: a naphthalene-based epoxy resin; an epoxy resin curing agent; and a polyimide resin or a polyimide amide imide Resin, soluble in a solvent having a boiling point of 150°C or lower, and wherein the naphthalene-based epoxy resin has an equivalent weight of 160 or less, wherein when the naphthalene-based epoxy resin and the epoxy resin When the sum of the weights of the resin curing agent is 100 parts by weight, the content of the polyimide resin or the polyimide amide imine resin is 5 to 50 parts by weight, and wherein the resin layer has 70% Or higher than 70% curing degree.

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