KR20170105275A - Metal laminate and printed circuit board comprising the same - Google Patents

Abstract

The present invention relates to a metal laminator including a resin layer composed of a polyimide resin composite and a printed circuit board (PCB) with the same. A withstanding voltage of the metal laminator is excellent, thus the present invention is able to provide the PCB with improved bendability. The metal laminator includes a metal layer and the resin layer equipped in the metal layer. The metal layer is formed of the polyimide resin composite including a first inorganic filler, a second inorganic filler, and a third inorganic filler. The first inorganic filler is aluminum oxide, the second inorganic filler is boron nitride, and the third inorganic filler is aluminum nitride.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a metal laminate and a printed circuit board including the metal laminate.

The present invention relates to a metal laminate including a resin layer made of a polyimide resin composition and a printed circuit board comprising the metal laminate.

2. Description of the Related Art As electronic devices have become thinner and denser, the development of flexible printed circuit boards (FPCB) that are slim and easy to install has been made variously. The flexible printed circuit board is composed of a metal layer on which a circuit pattern is formed and a resin layer serving as an insulating layer, and the resin layer is present on one side or both sides of the metal layer as a basic structure.

Such a flexible printed circuit board is required to have excellent bending. However, as the calorific value of electronic equipment increases, there is a limit to obtaining a required bending property. In other words, as the electronic devices have been made thinner and denser and densified, the amount of heat generated by electronic devices has been increased, and a flexible printed circuit board having excellent heat dissipation has been required to improve the heat generation. In this case, the inorganic filler having thermal conductivity is introduced into the resin layer serving as an insulating layer to improve the heat radiation property of the flexible printed circuit board. The heat dissipation of the flexible printed circuit board is improved by introducing the inorganic filler. However, There is a problem that the bending property of the flexible printed circuit board is lowered as the mechanical strength of the flexible printed circuit board increases.

Therefore, development of a flexible printed circuit board not only having heat dissipation but also excellent in bending property is required.

Korean Patent Publication No. 2012-0077440

In order to solve the above-described problems, it is an object of the present invention to provide a metal laminate excellent in heat resistance, adhesiveness, heat radiation and bending properties.

It is another object of the present invention to provide a printed circuit board comprising the metal laminate.

According to an aspect of the present invention, there is provided a semiconductor device comprising: a metal layer; And a resin layer provided on the metal layer, wherein the resin layer is formed of a polyimide resin composition comprising a first inorganic filler, a second inorganic filler, and a third inorganic filler, A D522 standard provides a metal laminate having an withstand voltage of 1.5 KV or higher in a withstand voltage evaluation.

Such a metal laminate of the present invention may exhibit an adhesive strength of 1.6 kgf / cm or more when evaluated in terms of an adhesive strength according to ASTM D2861 standard after being left at a temperature of 121 ° C and a pressure of 2 atm for 10 hours.

The first inorganic filler may be alumina, the second inorganic filler may be boron nitride, and the third inorganic filler may be aluminum nitride.

The mixing ratio (a: b: c) of the first inorganic filler (a) to the second inorganic filler (b) to the third inorganic filler (c) is 20 to 50: 1 to 15:20 to 50 Weight ratio.

The polyimide resin composition may further contain an aromatic diamine; Aromatic tetracarboxylic dianhydrides; And an organic solvent, and the aromatic diamine may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

,

,

및

로 표시되는 구조로 이루어진 군에서 선택된다.X and Y are the same or different from each other, and each independently,

,

,

And

As shown in FIG.

Here, the polyimide resin composition comprises 7.9 to 23.2% by weight of the first inorganic filler, the second inorganic filler, and the third inorganic filler based on 100% by weight of the polyimide resin composition; 7.5 to 9 wt% of the aromatic diamine; 7.8 to 9.4 wt% of the aromatic tetracarboxylic dianhydride; And 61.5 to 73.7% by weight of the organic solvent.

The present invention also provides a printed circuit board comprising the metal laminate.

Since the metal laminate of the present invention has a withstand voltage of 1.5 KV or more in a state of bending at a radius of 2Φ, when a printed circuit board is manufactured using the metal laminate, the bending property (or flexibility) A circuit board can be provided.

Hereinafter, the present invention will be described.

1. Metal The laminate

The present invention provides a metal laminate having excellent bending properties as the withstand voltage is high. The metal laminate of the present invention includes a metal layer; And a resin layer provided on the metal layer, which will be described in detail as follows.

The metal layer (first metal layer) included in the metal laminate of the present invention is a layer on which a circuit pattern is formed. The material constituting such a metal layer is not particularly limited, but copper, tin, gold or silver is preferable.

The resin layer included in the metal laminate of the present invention is provided on the metal layer as a layer serving as an insulating layer. Such a resin layer is formed of a polyimide resin composition composed of a specific component. That is, the resin layer of the present invention is formed of a polyimide resin composition in which an inorganic filler and a polyimide resin varnish solution are mixed, wherein the inorganic filler has a characteristic component and various particle sizes, and the polyimide resin varnish solution has a specific component And an aromatic diamine, which will be described in detail as follows.

The polyimide resin composition of the present invention comprises a plurality of inorganic fillers, that is, a first inorganic filler, a second inorganic filler, and a third inorganic filler.

The first inorganic filler is not particularly limited, but is preferably alumina excellent in thermal conductivity. At this time, it is preferable that the alumina has a spherical shape of particles and a mixture of a first alumina having a particle diameter of 0.3 to 0.6 mu m and a second alumina having a particle diameter of 2.3 to 4.1 mu m. When alumina mixed with the first alumina and the second alumina having different particle diameters is used, alumina particles having a small particle diameter are arranged between the alumina particles having a large particle diameter to form alumina particles or other inorganic fillers (the second and / Fillers) can be improved.

The second inorganic filler is not particularly limited, but is preferably boron nitride having a particle diameter of 0.2 to 1 占 퐉.

The third inorganic filler is not particularly limited, but is preferably aluminum nitride having a spherical shape and a particle size of 10 to 25 탆.

The mixing ratio of the first inorganic filler, the second inorganic filler, and the third inorganic filler contained in the polyimide resin composition of the present invention is not particularly limited, but in consideration of the physical properties of the resin layer, it is preferable that the mixing ratio (a: b: c) of the second inorganic filler (a) to the third inorganic filler (c) is 20: 50: 1 to 15:20: 50. Specifically, when the polyimide resin composition of the present invention contains the first alumina, the second alumina, the boron nitride and the aluminum nitride as the inorganic filler, the mixing ratio thereof is not particularly limited, The mixing ratio of the second alumina to the boron nitride to the aluminum nitride is preferably in a weight ratio of 5 to 12: 32 to 44: 5 to 12: 32 to 44.

Such a polyimide resin composition of the present invention comprises aromatic diamine; Aromatic tetracarboxylic dianhydrides; And a polyimide varnish solution containing an organic solvent. Since the aromatic diamine and the aromatic tetracarboxylic dianhydride are included, it is possible to improve not only the heat resistance, the adhesiveness and the heat radiation of the resin layer but also the bending property. In particular, when the aromatic diamine comprises a diamine having at least one ester group (a compound represented by the following formula (1)), when a resin layer (polyimide resin film) is formed with a polyimide varnish solution containing the same, Of 20% or more and a breaking strength of 100 MPa or more can be obtained. As a result, the resin layer of the present invention can exhibit flexible bending properties without breaking the resin layer even when a large number of inorganic fillers are introduced have.

The aromatic diamine contained in the polyimide resin composition of the present invention is not particularly limited, but is preferably at least one selected from the group consisting of compounds represented by the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

,

,

및

로 표시되는 구조로 이루어진 군에서 선택되고,X and Y are the same or different from each other, and each independently,

,

,

And

Lt; RTI ID = 0.0 > 1, < / RTI >

,

,

,

,

및

로 표시되는 구조로 이루어진 군에서 선택된다.A and B are the same or different from each other, and each independently,

,

,

,

,

And

As shown in FIG.

The compound represented by Formula 1 is not particularly limited, but 4-aminophenyl-4-aminobenzoate (APAB) is preferable. Since the 4-aminophenyl-4-aminobenzoate has a crystalline structure, crystallinity is imparted to the polyimide resin film having a semi-crystalline structure to increase the thermal conductivity of the resin layer.

The compound represented by the general formula (2) is not particularly limited, and examples thereof include 2,2-bis (4- (4-aminophenoxy) phenyl) propane, BAPP ), 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, m-BAPS) and 4,4'-bis 4,4'-bis (4-aminophenoxy) biphenyl) is preferable. The compound represented by the above formula (3) is not particularly limited, but 2,2 '- (1,2-phenylenebis (oxy)) dianiline, APBN ), (2,2'-dimethyl-4,4'-diaminobiphenyl, m-TB-HG), 1,3-bis (4-aminophenoxy) benzene, TPE-R). The use of the above compound increases the dispersibility or solubility with an organic solvent This is because the production of the polyimide resin film is facilitated.

Here, the mixing ratio of the compound represented by Formula 1 (first aromatic diamine) and the compound represented by Formula 2 or 3 (second aromatic diamine) is not particularly limited, It is preferable that the molar ratio is 3: 7 to 7: 3 based on the total number of moles. This is because not only the thermal conductivity of the resin layer can be improved by mixing at the above-mentioned molar ratio, but also the coating property of the polyimide resin composition can be improved.

The aromatic tetracarboxylic dianhydride contained in the polyimide resin composition of the present invention is not particularly limited, but 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (3,3', 4 , 4'-benzophenonetetracarboxylic dianhydride (BTDA), 2,2-bis (3,4-dicarboxyphenoxy) phenylpropane dianhydride, BPADA), 2,2- (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 6-FDA, pyromellitic dianhydride (PMDA) and 4,4-anhydrodicarboxyphenyl hexafluoropropane (4,4'-oxydiphthalic anhydride, ODPA). [0035] The term " oxydiphthalic anhydride " This is because the use of such an aromatic tetracarboxylic dianhydride can increase the adhesion of the resin layer.

The use ratio (mixing ratio) of the aromatic diamine and the aromatic tetracarboxylic dianhydride contained in the polyimide resin composition of the present invention is not particularly limited, but the molar ratio (a) of the aromatic diamine to the aromatic tetracarboxylic dianhydride (A: b) of the number of moles of the compound (b) is preferably 1 to 1.05: 1.

The organic solvent contained in the polyimide resin composition of the present invention is not particularly limited as long as it is well known in the art, and examples thereof include N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran ), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), cyclohexane and acetonitrile.

The content of each component in the polyimide resin composition of the present invention is not particularly limited. However, considering the physical properties of the resin layer, it is preferable that the inorganic filler (the first inorganic filler + Total amount of filler + third inorganic filler) 7.9 to 23.2% by weight; 7.5 to 9% by weight of aromatic diamine; Aromatic tetracarboxylic dianhydride 7.8 to 9.4% by weight; And a residual organic solvent that satisfies 100 wt% of the composition. At this time, the content of the organic solvent is preferably 61.5 to 73.7% by weight.

The metal laminate of the present invention including the resin layer formed of such a polyimide resin composition exhibits an internal withstand voltage of 1.5 KV or higher when the withstand voltage is evaluated in accordance with ASTM D522 in a bending state with a radius of 2Φ. As described above, since the dielectric strength of the metal laminate of the present invention is high even after bending, the metal laminate of the present invention can be effectively used in the production of a printed circuit board which requires excellent bending property.

Meanwhile, the metal laminate of the present invention may further include a metal layer (second metal layer) on the resin layer. Such a metal layer is a layer in which a circuit pattern is formed or a heat dissipation layer, and the material of the metal layer is not particularly limited, but copper, tin, gold or silver is preferable.

Further, the metal laminate of the present invention may further include the resin layer described above under the metal layer (first metal layer). That is, the metal laminate of the present invention may have the structure of the first resin layer-metal layer-second resin layer.

2. Printed Circuit Board

The present invention provides a printed circuit board comprising the above-described metal laminate. Specifically, the present invention provides a printed circuit board in which a circuit pattern is formed on a metal layer (a first metal layer and / or a second metal layer) included in the metal laminate. At this time, the resin layer included in the metal laminate serves as an insulating layer. Since the insulating layer of the printed circuit board of the present invention is formed of the polyimide resin composition described above, it has excellent physical properties such as heat resistance, adhesiveness, heat radiation, and excellent bending properties.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  1 to 4 and Comparative Example  1 to 3]

Resin compositions having the compositions and components shown in Table 1 below were prepared, respectively.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Epoxy resin 1
(Kukdo Chemical, YD-011) - - - - 2.0 g 2.5 g 2.7g Epoxy resin 2
(Kukdo Chemical, YD-019) - - - - 3.1 g 3.8 g 4.3 g Epoxy resin 3
(DOW, DER-383) - - - - 1.8 g 2.2 g 2.4 g Hardener
(EMomentive, DICY) - - - - 0.5 g 0.6 g 0.7g Diamine BAPP 2.9 g 3.1 g 3.2 g 2.7g - - - 0.26 mol 0.26 mol 0.26 mol 0.26 mol - - - APBN 2.1 g 2.2 g 2.3 g 1.9 g - - - 0.26 mol 0.26 mol 0.26 mol 0.26 mol - - - APAB 3.2 g 3.4 g 3.5 g 2.9 g - - - 0.50 mol 0.50 mol 0.50 mol 0.50 mol - - - Aromatic tetracarboxylic dianhydride ODPA 6.8 g 7.1 g 7.5g 6.2g - - - 0.80 mol 0.80 mol 0.80 mol 0.80 mol - - - BTDA 1.8 g 1.9 g 1.9 g 1.6 g - - - 0.20 mol 0.20 mol 0.20 mol 0.20 mol - - 1st weapon
filler Sumitomo AA-03
(Particle size: 0.3 mu m) 1.7 g 1.2 g 0.8 g 2.3 g 20.5 g 5.5 g 0.9 g Sumitomo AA-3
(Particle size: 3 mu m) 6.5 g 4.7 g 3.2 g 9.3 g 13.6 g 7.3 g 3.5 g The second weapon
filler Momentive NX-1
(Particle diameter: 1 占 퐉) 1.7 g 1.2 g 0.8 g 2.3 g - 5.4 g 0.9 g Third weapon
filler Toyo, TFZ A15
(Particle diameter: 15 mu m) 6.6 g 4.6 g 3.1 g 9.3 g - - 3.4 g NMP 66.7 g 70.6 g 73.7g 61.5 g 58.5g 72.7g 81.2 g

[ Manufacturing example  1 to 5 and Comparative Manufacturing Example  1 to 3] metal The laminate  Produce

After the respective resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were applied to a copper foil having a thickness of 35 占 퐉 in a thickness of 100 占 퐉, the resin compositions of Examples 1 to 4 were evaluated at 200 占 폚, 3 was dried at 150 DEG C for about 1 hour to form a resin layer. Next, an aluminum foil having a thickness of 2 mm was laminated on the resin layer, and then pressed at 220 DEG C and 100 MPa for 1 hour to produce metal laminate bodies, respectively.

[ Experimental Example  1] Metal The laminate  Property evaluation

The physical properties of the metal laminates prepared in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 3 were evaluated by the following methods, and the results are shown in Table 2 below.

1. Thermal Conductivity: The thermal conductivity of the resin layer was evaluated according to ASTM D5470 standard.

2. Heat resistance: The metal laminate was placed on a 288 ° C water bath and the time for blistering was measured.

3. Withstanding voltage before bending: The metal laminate was evaluated according to ASTM D522 standard.

4. Durability after bending: The metal laminate was evaluated in accordance with ASTM D522 standard with a bending radius of 2Φ.

5. Bending properties: The results were evaluated as 'good' when the withstand voltage after bending was over 1 KV, and 'bad' when it was below 1 KV.

6. Adhesion strength: The metal laminate was left at a temperature of 121 캜 and a pressure of 2 atm for 10 hours, and then evaluated according to ASTM D2861 standard.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 compare
Production Example 1 compare
Production Example 2 compare
Production Example 3 Thermal conductivity (W / mK) 2 1.8 1.6 2.5 0.9 1.1 1.4 Heat resistance
(S / D @ 288) > 10 min > 10 min > 10 min > 10 min > 10 min > 10 min > 10 min Withstanding voltage before bending (KV) 5.1 5.5 5.6 5.3 4.2 4.5 4.9 Withstanding voltage after bending (KV) 2.9 3.1 3.5 2.8 0.1 0.2 0.9 Bending property good good good good Poor Poor Poor Adhesion (@ 1 Oz-kgf / cm) 1.7 1.9 2.0 1.6 1.1 1.3 1.4

Referring to Table 2, it can be seen that the metal laminate of the present invention has excellent physical properties because the resin layer is made of the resin compositions of Examples 1 to 4. In particular, it can be confirmed that Production Examples 1 to 4 of the metal laminate of the present invention have excellent bending properties as the withstand voltage after bending is 1.5 KV or more.

Claims (7)

A metal layer; And
And a resin layer provided on the metal layer,
Wherein the resin layer is formed of a polyimide resin composition comprising a first inorganic filler, a second inorganic filler, and a third inorganic filler,
A metal laminate having a withstand voltage of 1.5 KV or higher when the withstand voltage is evaluated in accordance with ASTM D522 while bending at a radius of 2Φ. The method according to claim 1,
A metal laminate exhibiting an adhesive strength of 1.6 kgf / cm or more in the adhesive strength evaluation according to ASTM D2861 standard after being left at a temperature of 121 占 폚 and a pressure of 2 atm for 10 hours. The method according to claim 1,
Wherein the first inorganic filler is alumina, the second inorganic filler is boron nitride, and the third inorganic filler is aluminum nitride. The method according to claim 1,
Wherein the mixing ratio (a: b: c) of the first inorganic filler (a) to the second inorganic filler (b) to the third inorganic filler (c) is 20 to 50: 1 to 15:20 to 50 Metal laminate. The method according to claim 1,
Wherein the polyimide resin composition comprises an aromatic diamine; Aromatic tetracarboxylic dianhydrides; And an organic solvent,
Wherein the aromatic diamine comprises a compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
X and Y are the same or different from each other, and each independently,

,

,

And

As shown in FIG. 6. The method of claim 5,
The polyimide resin composition may contain, based on 100 wt% of the polyimide resin composition,
7.9 to 23.2% by weight of the first inorganic filler, the second inorganic filler, and the third inorganic filler;
7.5 to 9 wt% of the aromatic diamine;
7.8 to 9.4 wt% of the aromatic tetracarboxylic dianhydride; And
And 61.5 to 73.7% by weight of the organic solvent. A printed circuit board comprising the metal laminate of any one of claims 1 to 6.