KR101566836B1 - Metallic laminate and method for preparing the same - Google Patents

Abstract

At least one metal layer; And a polyimide resin layer having a low dielectric constant including a polyimide resin and a silane compound. According to the present invention, a metal laminate including a polyimide resin layer having a low dielectric constant including a silane compound and having excellent heat resistance and dimensional stability can be provided.

Description

METAL LAMINATE AND METHOD FOR PREPARING THE Same,

The present invention relates to a metal laminate and a method of manufacturing the same. More particularly, the present invention relates to a metal laminate including a polyimide resin layer having a low dielectric constant and excellent in heat resistance and dimensional stability, and a method for producing the same.

In recent years, the speed of signal transmission between electronic devices and external devices has been increasing in accordance with the trend of miniaturization and speedup of electronic devices and the combination of various functions. 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, in the flexible metal laminate, the circuit boards used in electronic equipment are required to have higher densities as a result of miniaturization and multifunctionalization of electronic apparatuses, particularly, light-weight and shortening of portable apparatuses. In order to meet such demands, . For this purpose, if the thickness of the metal layer is reduced, a fine pattern can be formed. However, due to the high dielectric constant of the polyimide as the insulating layer, a limit of the fine pattern is generated. That is, when a flexible metal laminate having a polyimide resin layer is used for an electronic device in a high frequency range, there is a problem that reliability is lowered due to noise generation. Therefore, polyimide is required to have low dielectric constant and low dielectric loss factor as electrical characteristics corresponding to high speed.

To solve this problem, it is necessary to increase the thickness of the insulating layer or to introduce an insulating layer having a low dielectric constant. For example, Korean Patent Publication No. 2004-0095663 discloses a metal laminate comprising an insulating layer exhibiting a low dielectric constant using a polyimide resin having a specific structure.

Alternatively, a flexible copper-clad laminate using a liquid crystal polymer having a low dielectric constant in addition to polyimide has been produced. However, the liquid crystal polymer is not preferable because heat resistance and dimensional stability are not superior to polyimide.

Accordingly, a printed circuit board using an insulator having a lower permittivity and a lower dielectric loss coefficient than conventional insulators is required.

It is an object of the present invention to provide a metal laminate including a polyimide resin layer exhibiting a low dielectric constant while maintaining excellent physical properties.

It is another object of the present invention to provide a method for producing the metal laminate.

In order to achieve the above object, the present invention provides a semiconductor device comprising at least one metal layer; And a low dielectric constant polyimide resin layer comprising a first polyimide resin and a silane compound.

According to an embodiment of the present invention, the low dielectric constant polyimide resin layer may have a dielectric constant of 2.5 to 3.0.

According to an embodiment of the present invention, the silane compound may be included in an amount of 10 to 200 parts by weight based on 100 parts by weight of the first polyimide resin.

According to an embodiment of the present invention, the silane compound may be an alkoxysilane compound containing an aromatic hydrocarbon.

According to an embodiment of the present invention, the metal laminate may further include a thermoplastic polyimide resin layer.

According to an embodiment of the present invention, when the metal laminate further includes a thermoplastic polyimide resin layer, the low dielectric constant polyimide resin layer and the thermoplastic polyimide resin layer include two metal layers opposed to each other, Can be sequentially positioned between the two metal layers.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying a first resin composition comprising a first diamine component, a first dianhydride component, and a silane compound on one surface of a metal layer; And thermally curing the applied first resin composition to form a low dielectric constant polyimide resin layer.

The present invention also provides a method of manufacturing a semiconductor device, comprising: applying a first resin composition comprising a first diamine component, a first dianhydride component, and a silane compound onto one surface of a first metal layer; Applying a second resin composition comprising a second diamine component and a second dianhydride component on a coating surface of the first resin composition; Thermally curing the applied first and second resin compositions to form a low dielectric constant polyimide resin layer and a thermoplastic polyimide resin layer; And heating and pressing the second metal layer on the thermoplastic polyimide resin layer.

According to an embodiment of the present invention, the step of thermally curing the applied first and second resin compositions may be performed at 200 to 400 ° C for 2 to 60 minutes.

According to an embodiment of the present invention, the step of heating and pressing the second metal layer may be performed at 300 to 390 ° C.

According to the present invention, a metal laminate having excellent heat resistance and dimensional stability can be provided by including a low dielectric constant polyimide resin layer containing a silane compound.

The metal laminate of the present invention comprises at least one metal layer; And a low dielectric constant polyimide resin layer comprising a first polyimide resin and a silane compound.

The method for producing a metal laminate according to the present invention comprises the steps of applying a resin composition comprising a first diamine component, a first dianhydride component and a silane compound on one surface of a metal layer and thermally curing the applied resin composition And forming a dielectric constant polyimide resin layer.

Another method for producing a metal laminate of the present invention comprises: applying a first resin composition comprising a first diamine component, a first dianhydride component, and a silane compound onto one surface of a first metal layer; Applying a second resin composition comprising a second diamine component and a second dianhydride component on a coating surface of the first resin composition; Thermally curing the applied first and second resin compositions to form a low dielectric constant polyimide resin layer and a thermoplastic polyimide resin layer; And hot pressing the second metal layer on the thermoplastic polyimide resin layer.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Also in the present invention, when each layer is referred to as being "on" or "on" each layer, it means that each layer is formed directly on each layer, or that another layer is formed between each layer, As shown in FIG.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, a metal laminate according to a specific embodiment of the present invention and a method of manufacturing the metal laminate will be described in more detail.

metal The laminate

The metal laminate of the present invention includes at least one metal layer and a low dielectric constant polyimide resin layer including a first polyimide resin and a silane compound.

According to an embodiment of the present invention, the metal layer may include at least one of Cu, Al, Fe, Ag, Pd, Ni, Cr, Mo, ), Tungsten (W), zinc (Zn), stainless steel, and alloys thereof, and preferably copper foil used for the PCB. If necessary, a chemical or mechanical surface treatment may be applied to the surface of the metal layer.

The thickness of the metal layer is not particularly limited but may be about 5 to about 50 占 퐉, preferably about 8 to about 35 占 퐉.

According to an embodiment of the present invention, the metal laminate may be a cross-section metal laminate including a low dielectric constant polyimide resin layer formed on one metal layer. At this time, another polyimide resin layer may be further interposed between the low dielectric constant polyimide resin layer and the metal layer.

According to another embodiment of the present invention, the metal laminate may be a double-sided metal laminate having a low dielectric constant polyimide resin layer and a thermoplastic polyimide resin layer laminated between two metal layers opposed to each other. In this case also, another polyimide resin layer may be further provided between the low dielectric constant polyimide resin layer and the metal layer, or between the thermoplastic polyimide resin layer and the metal layer.

The metal laminate of the present invention includes a low dielectric constant polyimide resin layer, and the low dielectric constant polyimide resin layer may be formed on one side of the metal layer.

The low dielectric constant polyimide resin layer is an insulating layer of the metal laminate It is a functional base layer. In recent years, there has been a demand for high-speed transmission of information in accordance with high performance and high performance of electronic devices, and it is required that components used in these devices exhibit low dielectric constant as electrical characteristics corresponding to high speed. As a method for lowering the dielectric constant of the polyimide resin, there is a method of changing the structure itself by introducing a specific substituent to the polyimide resin. However, such a method may lower the adhesion to the metal layer and other mechanical properties.

The low-dielectric-constant polyimide resin layer included in the metal laminate of the present invention includes the first polyimide resin and the silane compound so that a dielectric constant of about 3.0 or less, preferably about 2.5 to about 3.0 It can have a dielectric constant. Since the low-dielectric-constant polyimide resin layer has a dielectric constant of 3.0 or less, when the metal laminate including the low-dielectric-constant polyimide resin layer is used for a flexible printed circuit board, noise can be reduced and the reliability of the electronic circuit can be maintained.

Further, the low dielectric constant polyimide resin layer may have a coefficient of linear thermal expansion of 30 ppm / K or less, preferably about 15 ppm / K to about 25 ppm / K. The low-dielectric-constant polyimide resin layer has a coefficient of linear thermal expansion of less than a certain level, thereby minimizing the curl phenomenon of the substrate due to thermal stress generated during the process of thermally curing and cooling the polyamic acid, which is a precursor of the polyimide resin And thus, the quality and reliability of the final product can be prevented from being greatly deteriorated.

In the metal laminate of the present invention, the low dielectric constant polyimide resin layer includes a first polyimide resin and a silane compound.

The 1 polyimide resin may be formed by curing a 1-polyamic acid solution which is a precursor obtained by reacting a first diamine component with a first dianhydride component.

The first diamine component is not particularly limited, and for example, p-phenylenediamine (m-PDA), 4,4'-oxydianiline (4,4'-ODA: 4,4'- oxydianiline, 3,4'-oxydianiline, 2,2-bis (4- [4- aminophenoxy] -phenyl) propane (BAPP: 2 , 2-bis (4- [4-aminophenoxy] -phenyl) propane, 2,2'-dimethyl-4,4'- diaminobiphenyl (m- 4'-diamino biphenyl, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- [ ] Phenyl) sulfone (m-BAPS: 2,2-bis- (4- [3-aminophenoxy] phenyl) sulfone), 4,4'-diaminobenzanil (DABA), 4,4'-diamino benzanilide, 4,4'-bis (4-aminophenoxy) biphenyl (4-aminophenoxy) biphenyl ) biphenyl or 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diaminobiphenyl (TFDB: 2,2'-bis Can be used.

Further, the first dianhydride component is not particularly limited, and for example, Pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA: 3,3', 4,4'-benzophenonetetracarboxylic dianhydride), 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA: 3,4' -biphenyltetracarboxylic dianhydride), 4,4'-oxydiphthalic anhydride (ODPA: 4 , 4'-oxydiphthalic anhydride, 4,4 '- (4,4'-isopropylidene diphenoxy) -bis- (phthalic anhydride) (BPADA: isopropylidenediphenoxy) -bis- (phthalic anhydride), 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA: 2,2'- ) hexafluoropropane dianhydride (TMEG), ethyleneglycolbis (anhydro-trimellitate), or 3,4-3 ', 4'-diphenylsulfone tetracarboxylic dianhydride (DSDA: 3,4-3 ', 4'-diphenylsulfone tetracarboxylic dianhydride) .

The silane compound contained in the low-dielectric-constant polyimide resin layer is preferably an alkoxysilane compound, particularly an alkoxysilane compound containing an aromatic hydrocarbon. For example, according to one embodiment of the present invention, there may be mentioned 3-aminophenyl trimethoxysilane, 4-aminophenyl trimethoxysilane, 3-aminophenyl triethoxy silane, 4-aminophenyl triethoxysilane, phenyl trimethoxysilane, or phenyl triethoxysilane may be used as the silane coupling agent.

The silane compound may be included in an amount of about 10 to about 200 parts by weight, preferably about 10 to about 150 parts by weight, and more preferably about 20 to about 100 parts by weight based on 100 parts by weight of the first polyimide resin. If the amount of the silane compound is less than 10 parts by weight, a desired low dielectric constant can not be obtained. If the silane compound is used in excess of 200 parts by weight, the strength of the polyimide resin layer may be weakened and torn or broken.

The thickness of the low dielectric constant polyimide resin layer is not particularly limited, but may be about 5 to about 200 占 퐉, preferably about 9 to about 150 占 퐉.

According to another embodiment of the present invention, the metal laminate may further include a thermoplastic polyimide resin layer. At this time, the metal laminate includes two metal layers opposed to each other, and the low dielectric constant polyimide resin layer and the thermoplastic polyimide resin layer may be a double-sided metal laminate sequentially disposed between the two metal layers.

The thermoplastic polyimide resin layer is a layer which functions as an insulating layer having high heat resistance by increasing the bonding strength with the metal layer when the metal layer is heat-pressed in the double-side metal laminate.

In the metal laminate of the present invention, the thermoplastic polyimide resin layer is not particularly limited as long as it can laminate the metal layer by hot pressing, but it is preferable that the glass transition temperature is in the range of A polyimide resin having a temperature of about 200 DEG C or higher, preferably about 250 DEG C to about 300 DEG C can be used. Also, the coefficient of linear thermal expansion may be 30 ppm / K or more, preferably about 40 to about 70 ppm / K. By including the thermoplastic polyimide resin layer having such physical properties as described above, it is possible to satisfy the high characteristics of the metal laminate such as soldering heat resistance and reflow to environmental changes of temperature and humidity.

The thermoplastic polyimide resin layer is formed by curing a second polyamic acid resin solution which is a precursor. The second polyamic acid resin is obtained by reacting a second diamine component with a second dianhydride component. The second diamine component and the second dianhydride component may be the same as or different from the first diamine component and the first dianhydride component used in the low-dielectric-constant polyimide resin layer, respectively.

The second diamine component is not particularly limited, and for example, p-phenylenediamine, m-phenylenediamine, 4,4'-oxydianiline, 3,4'-oxydianiline, 2,2-bis (4- [ Bis (4-aminophenoxy) phenyl) sulfone (hereinafter, referred to as " (4-aminophenoxy) phenyl) sulfone, 4,4'-diaminobenzanilide, 4,4'-bis (4-aminophenoxy) biphenyl, or 2,2'- Methyl) biphenyl-4,4'-diaminobiphenyl, and the like.

The second dianhydride component is not particularly limited, and for example, Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dihalide, 4,4' -Oxydiptalic anhydride, 4,4 '- (4,4'-isopropylidene diphenoxy) -bis- (phthalic anhydride), 2,2'-bis- Carboxyphenyl) hexafluoropropane dianhydride, ethylene glycol bis (anhydro-trimellitate), or 3,4-3 ', 4'-diphenylsulfone tetracarboxylic dianhydride.

The thickness of the thermoplastic polyimide resin layer is not particularly limited but may be about 1 to about 50 占 퐉, preferably about 2 to about 25 占 퐉.

The metal laminate according to the present invention can be produced according to necessity in order to reduce the occurrence of curl and increase adhesion to the metal layer And may further include a polyimide resin layer. The polyimide resin layer may be located between the metal layer and the low dielectric constant polyimide resin layer, between the low dielectric constant polyimide resin layer and the thermoplastic polyimide resin layer, or anywhere on the thermoplastic resin layer, According to an embodiment of the present invention, the metal layer and the low dielectric constant polyimide resin layer are located between the metal layer and the low dielectric constant polyimide resin layer.

The polyimide resin layer is formed by curing a solution of a third polyamic acid resin which is a precursor. The third polyamic acid resin is obtained by reacting a third diamine component and a third dianhydride component. The third diamine component may be the same as or different from the first and second diamine components used in the low-dielectric-constant polyimide resin layer or the thermoplastic polyimide resin layer. Likewise, the tertiary dihydride component may be the same or different from the first and second dianhydride components, respectively.

Since the low dielectric constant polyimide resin layer of the metal laminate of the present invention has a low dielectric constant, generation of noise can be minimized. In addition, the thermoplastic polyimide resin layer minimizes warpage in the manufacturing process of the flexible printed circuit board. Therefore, the metal laminate of the present invention can be provided on a flexible printed circuit board having high heat resistance and dimensional stability as well as excellent quality and reliability.

metal Of the laminate  Manufacturing method

The method for producing a metal laminate of the present invention comprises the steps of: applying a first resin composition comprising a first diamine component, a first dianhydride component and a silane compound onto one surface of a metal layer; And thermally curing the applied first resin composition to form a low dielectric constant polyimide resin layer.

Specifically, the first polyamic acid can be prepared by dissolving the first diamine component and the first dianhydride component in a solvent. The reaction of the first diamine component with the first dianhydride is initiated at a temperature of about 80 DEG C or below, preferably about 0 DEG C to about 5 DEG C, until the reaction is completed in a temperature range of about 10 DEG C to about 40 DEG C It can be performed around 24 hours. At this time, the first diamine component and the first dianhydride may be mixed at a molar ratio of 1: 0.9 to 1: 1.1. If the molar ratio is less than 1: 0.9, the molecular weight becomes too low to produce polyamic acid having excellent mechanical properties. On the other hand, if the molar ratio exceeds 1: 1.1, the viscosity becomes too high and various processes required for coating and working become difficult.

A detailed description of the first diamine component and the first dianhydride component is as described above in the description of the low dielectric constant polyimide resin layer of the metal laminate.

In order to facilitate application or curing or to improve other physical properties, additives such as antioxidants, curing accelerators and the like may be further added as necessary.

The silane compound contained in the first resin composition is preferably an alkoxysilane compound, particularly an alkoxysilane compound containing an aromatic hydrocarbon. Examples of the aromatic hydrocarbon-containing alkoxysilane compound include 3-aminophenyl trimethoxysilane, 4-aminophenyl trimethoxysilane, 3-aminophenyl triethoxy silane, 4-aminophenyl triethoxysilane, phenyl trimethoxysilane, or phenyl triethoxysilane can be given as examples of the aminophenyl triethoxysilane, 3-aminophenyl triethoxysilane, 4-aminophenyl triethoxysilane, phenyl trimethoxysilane and phenyl triethoxysilane.

The first resin composition may be used in the form of being dissolved in a solvent to improve the applicability. Examples of the solvent for dissolving the first resin composition include N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran At least one selected from the group consisting of THF (tetrahydrofuran), N, N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO).

As described above, the first resin composition including the first diamine component, the first dianhydride component, and the silane compound is applied to one surface of the metal layer. In the step of coating the first resin composition on the metal layer, a commonly used application method and apparatus can be used without limitation. For example, methods such as a spray method, a roll coating method, a rotation coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method or a knife coating method can be used.

Further, specific details regarding the material and thickness of the metal layer are as described above in the metal laminate.

According to one embodiment of the present invention, after the first resin composition is applied as described above, a drying method such as an arch type oven, a floating type oven, Lt; / RTI >

The first resin composition is dried and then thermally cured to produce a polyamic acid by the reaction of the first diamine component and the first dianhydride component in the first composition. By imidizing the polyamic acid, a low dielectric constant polyimide Thereby forming a resin layer.

According to one embodiment of the present invention, Lt; / RTI > and can be cured at this temperature for about 2 to about 60 minutes. If the temperature is too low, curing of the polyimide is not perfect, and if it is too high, pyrolysis may occur, which is not preferable. The curing may be carried out by gradually heating in an oven under a nitrogen atmosphere or a vacuum and curing, or continuously passing through a high temperature in a nitrogen atmosphere.

According to another embodiment of the present invention, there is provided a method of manufacturing a metal laminate, comprising: applying a first resin composition comprising a first diamine component, a first dianhydride component, and a silane compound onto one surface of a first metal layer ; Applying a second resin composition comprising a second diamine component and a second dianhydride component on a coating surface of the first resin composition; Thermally curing the applied first and second resin compositions to form a low dielectric constant polyimide resin layer and a thermoplastic polyimide resin layer; And hot pressing the second metal layer on the thermoplastic polyimide resin layer.

A detailed description of the step of applying the first resin composition containing the first diamine component, the first dianhydride component and the silane compound on one surface of the first metal layer is as described above.

Next, a second resin composition containing a second diamine component and a second dianhydride component is applied on the application surface of the first resin composition.

The second polyamic acid may be formed by the reaction of the second diamine component and the second dianhydride component. Specifically, the second polyamic acid can be prepared by dissolving the second diamine component and the second dianhydride component in a solvent and reacting.

The reaction of the second diamine component with the second dianhydride is initiated at a temperature of about 80 DEG C or lower, preferably about 0 DEG C to about 5 DEG C, until the reaction is completed in a temperature range of about 10 DEG C to about 40 DEG C It can be performed around 24 hours. At this time, the second diamine component and the second dianhydride may be mixed at a molar ratio of 1: 0.9 to 1: 1.1.

A detailed description of the second diamine component and the second dianhydride component is as described above in the description of the thermoplastic polyimide resin layer of the metal laminate.

The second resin composition comprising the second diamine component and the second dianhydride prepared as described above is applied on the application surface of the first resin composition. In the step of coating the first resin composition on the coated surface of the first resin composition, a commonly used coating method and apparatus can be used without limitation.

According to an embodiment of the present invention, a first resin composition comprising the first diamine component, the first dianhydride component, and the silane compound is applied, dried and thermally cured to form a low-dielectric-constant polyimide resin layer , A second resin composition containing the second diamine component and the second dianhydride may be applied, dried and thermally cured to form the thermoplastic resin layer in order.

According to another embodiment of the present invention, after the first resin composition is applied, the second resin composition is coated on the coated surface of the first resin composition, followed by drying, and then the dried materials of the first and second resin compositions are cured .

In order to form a resin layer having a simpler process design and uniform physical properties, it is preferable to thermoset the dried product of the first and second resin compositions in one step.

According to one embodiment of the present invention, after the second resin composition is applied as described above, it may be dried at a temperature lower than the boiling point of the solvent by using a drying means such as an arched oven, a floating oven, or the like.

Next, the first and second resin compositions are coated on one surface of the first metal layer, dried, and thermally cured to imidize the polyamic acid in the first and second resin compositions.

According to one embodiment of the present invention, Lt; / RTI > and can be cured at this temperature for about 2 to about 60 minutes. If the temperature is too low, curing of the polyimide is not perfect, and if it is too high, pyrolysis may occur, which is not preferable. The curing may be carried out by gradually heating in an oven under a nitrogen atmosphere or a vacuum and curing, or continuously passing through a high temperature in a nitrogen atmosphere.

Next, another second metal layer is thermally pressed on the cured polyimide resin layer. As another metal layer is heated and pressed, a double-side metal laminate in which a low-dielectric-constant polyimide resin layer and a thermoplastic polyimide resin layer are disposed between two opposing metal layers can be provided. That is, a double-side metal laminate in which a first metal layer, a low dielectric constant polyimide resin layer, a thermoplastic polyimide resin layer, and a second metal layer are stacked in this order can be formed.

Since moisture may be generated in the thermosetting step of the first and second resin compositions, the thermosetting step is preferably performed after the thermosetting step is completely completed.

The hot pressing step may be performed at about 300 to about 390 ° C. If the hot-pressing temperature is less than 300 ° C, the flowability of the thermoplastic resin is insufficient, and sufficient adhesion can not be obtained even if the hot-pressing is performed. If the hot-pressing temperature exceeds 390 ° C, wrinkles may occur in the metal layer.

The pressure applied during the hot pressing may be about 1 to about 100 kg / cm < ² >. If the pressure is too small, it is difficult to obtain a sufficient adhesive force, and if it is too large, cracks may be generated inside the metal laminate.

In addition, the means for hot pressing is not particularly limited, but can be carried out using a batch type press or a roll press type continuous process.

According to another embodiment of the present invention, before the first resin composition is applied on one surface of the first metal layer, a third resin comprising a third diamine component and a third dianhydride component on one surface of the first metal layer The method may further comprise applying the composition. Here, the detailed description of the third diamine component and the third dianhydride component is as described above in the metal laminate.

That is, before the first resin composition is applied on the first metal layer, the third resin composition including the third polyamic acid is first applied, and then the first resin composition is applied on the application surface of the third resin composition . The steps of application, drying and curing of the second resin composition and hot pressing of the second metal layer are as described above. A double-sided metal laminate in which a first metal layer, a polyimide resin layer, a low-dielectric-constant polyimide resin layer, a thermoplastic polyimide resin layer, and a second metal layer are stacked in this order can be formed according to the above-described manufacturing method.

Hereinafter, the present invention will be described in more detail by way of the following examples, but the scope of the present invention is not limited by the examples.

< Example >

Example  One

14.5 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 14.5 g of p-phenylenediamine (PDA) were added to a 1/3 oz. F2-WS copper foil manufactured by Furukawa, , 0.44 g of 3-aminophenyl trimethoxysilane, 8.35 g of phenyl trimethoxysilane, Was dissolved in N, N-dimethylacetamide in a concentration of 19 wt%, and the resultant was applied in a thickness of 130 탆, followed by drying in an oven at 140 캜 for 5 minutes.

After drying, a mixture of 1 mol of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1 mol of 1,3-bis (4-aminophenoxy) benzene (TPER) The resin composition was dissolved in N, N-dimethylacetamide in a concentration of 13 wt% and applied in a thickness of 20 탆, dried in an oven at 140 캜 for 2 minutes, treated at 200 캜 for 20 minutes, at 250 캜 for 4 minutes, And the mixture was gradually cooled to prepare a metal laminate. The produced metal laminate was heat-pressed with another laminator (1/3 oz, F2-WS copper foil manufactured by Furukawa) at a temperature of 380 캜 and a pressure of 50 kg / cm ² using a laminator to obtain a copper foil layer, A double-sided metal laminate having laminated layers of a laminate, a mid layer, a thermoplastic polyimide layer and another copper foil layer was prepared.

The physical properties of the prepared metal laminate were measured and are shown in Table 1.

Example  2

A 1/3 oz F2-WS copper foil manufactured by Furukawa Co., Ltd. was charged with 8.21 g of pyromellitic dianhydride (PMDA), 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diamino A first resin composition comprising 11.45 g of biphenyl (TFDB), 0.34 g of 3-aminophenyl trimethoxysilane, and 8.35 g of phenyl trimethoxysilane was dissolved in N, N-dimethylacetate Amide at a concentration of 19 wt% and applied in a thickness of 130 탆, followed by drying in an oven at 140 캜 for 5 minutes.

After drying, a mixture of 1 mol of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1 mol of 1,3-bis (4-aminophenoxy) benzene (TPER) The resin composition was dissolved in N, N-dimethylacetamide in a concentration of 13 wt% and applied in a thickness of 20 탆, dried in an oven at 140 캜 for 2 minutes, treated at 200 캜 for 20 minutes, at 250 캜 for 4 minutes, And the mixture was gradually cooled to prepare a metal laminate. The produced metal laminate was heat-pressed with another laminator (1/3 oz, F2-WS copper foil manufactured by Furukawa) at a temperature of 380 캜 and a pressure of 50 kg / cm ² using a laminator to obtain a copper foil layer, A double-sided metal laminate having laminated layers of a laminate, a mid layer, a thermoplastic polyimide layer and another copper foil layer was prepared.

The physical properties of the prepared metal laminate were measured and are shown in Table 1.

Comparative Example  One

1 mole of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1 mole of p-phenylenediamine (PDA) in a 1/3 oz F2-WS copper foil manufactured by Furukawa, 1 mole N, N-dimethylacetamide at a concentration of 17 wt% and applied in a thickness of 130 탆, followed by drying in an oven at 140 캜 for 5 minutes.

After drying, 1 mole of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1 mole of 1,3-bis (4-aminophenoxy) benzene (TPER) Dissolved in dimethylacetamide in a concentration of 13wt%, dried in an oven at 140 ° C for 2 minutes, passed at 200 ° C for 20 minutes, 250 ° C for 4 minutes, and 350 ° C for 8 minutes continuously at a high temperature Cured, and then slowly cooled to prepare a metal laminate. The prepared metal laminates were heat-pressed with other laminates prepared at a temperature of 380 DEG C and a pressure of 50 kg / cm &lt; ² &gt; by means of a laminator to produce a double-side metal laminate in which a copper foil layer, two polyimide layers and another copper foil layer were laminated.

The physical properties of the prepared metal laminate were measured and are shown in Table 1.

< Experimental Example >

How to measure property

One. Line thermal expansion  Coefficient

The metal laminate of the examples and comparative examples was heated to 200 DEG C using a TMA (thermo mechanical analyzer), held at the elevated temperature for 5 minutes, cooled and heated at a rate of 10 DEG C / min, The average coefficient of thermal expansion was calculated by the coefficient of linear thermal expansion.

2. Permittivity

The polyimide layer of the metal laminate of the examples and comparative examples was measured using the HP4194A device of HP by the method of IPC-TM-650.2.5.5.3, which is a PCB standard.

The coefficient of linear thermal expansion and dielectric constant measured by the above method are shown in Table 1 below.

division Coefficient of linear thermal expansion
(Unit: ppm / K) permittivity
(at 1 MHz) Example 1 20 2.9 Example 2 22 2.8 Comparative Example 1 18 3.3

Referring to Table 1, the dielectric constant and the coefficient of linear thermal expansion of Examples 1 and 2 including the silane compound in the low-dielectric-constant polyimide layer were excellent.

Claims (18)

Two metal layers opposed to each other;
Wherein the first metal layer is sequentially disposed between the two metal layers,
A first polyimide resin; And a low dielectric constant polyimide resin layer containing an alkoxysilane compound containing an aromatic hydrocarbon and having a dielectric constant of 2.5 to 3.0 and a coefficient of linear thermal expansion of 15 to 25 ppm / K; And
And a thermoplastic polyimide resin layer having a coefficient of linear thermal expansion of 40 to 70 ppm / K.
delete delete The method of claim 1, wherein the aromatic hydrocarbon-containing alkoxysilane compound is selected from the group consisting of 3-aminophenyl trimethoxysilane, 4-aminophenyl trimethoxysilane, (3-aminophenyl triethoxysilane), 4-aminophenyl triethoxysilane, phenyl trimethoxysilane, and phenyl triethoxysilane. A metal laminate comprising at least one member.
2. The metal laminate according to claim 1, wherein the aromatic hydrocarbon-containing alkoxysilane compound is contained in an amount of 10 to 200 parts by weight based on 100 parts by weight of the first polyimide resin.
The metal laminate according to claim 1, wherein the low dielectric constant polyimide resin layer has a thickness of 5 to 200 占 퐉.
delete delete The metal laminate according to claim 1, wherein the thermoplastic polyimide resin layer has a glass transition temperature of 250 to 300 캜.
delete delete delete delete delete Applying a first resin composition comprising a first diamine component, a first dianhydride component and an alkoxysilane compound comprising an aromatic hydrocarbon onto one surface of a first metal layer;
Applying a second resin composition comprising a second diamine component and a second dianhydride component on a coating surface of the first resin composition;
A low dielectric constant polyimide resin layer having a dielectric constant of 2.5 to 3.0 and a coefficient of linear thermal expansion of 15 to 25 ppm / K by thermally curing the applied first and second resin compositions; And a thermoplastic polyimide resin layer having a coefficient of linear thermal expansion of 40 to 70 ppm / K; And
And heating and pressing the second metal layer on the thermoplastic polyimide resin layer.
16. The method according to claim 15, wherein the thermosetting of the applied first and second resin compositions is performed at 200 to 400 DEG C for 2 to 60 minutes.
16. The method of claim 15, wherein the step of heating and pressing the second metal layer is performed at 300 to 390 占 폚.
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