KR20170076127A - Polyimide resin, metal laminate using the same and printed circuit board comprising the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin, a metal laminate using the same, and a printed circuit board comprising the same, and the polyimide resin has excellent thermal conductivity.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide resin, a metal laminate using the same, and a printed circuit board comprising the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a polyimide resin used as an insulating layer, a metal laminate using the polyimide resin, and a printed circuit board including the metal laminate.

As the electronic devices become more sophisticated and slimmer and thinner, the amount of heat generated by electronic components is increasing. Also, with the emergence of new and renewable energy and the demand for increasing energy efficiency, the use of high voltage high power devices is increasing, and especially in such high power devices, heat generation has a great influence on safety and device life . Accordingly, there is an increasing need for a printed circuit board capable of efficiently emitting heat generated in the apparatus.

In the conventional printed circuit board, an epoxy resin is applied to the insulating layer. The epoxy resin is excellent in strength, insulation, heat resistance and adhesiveness, but has a low thermal conductivity and thus has a limitation in efficiently discharging heat generated in a device connected to a printed circuit board.

Accordingly, a technique of introducing an inorganic filler into an epoxy resin has been proposed in order to improve the thermal conductivity of the epoxy resin. However, this technique has a problem that the processability (drillability) and the bending property of the printed circuit board are lowered as the inorganic filler is used in a high content to obtain the required thermal conductivity.

Korean Patent Laid-Open Publication No. 2014-0037552

In order to solve the above problems, it is an object of the present invention to provide a polyimide resin having not only insulation, heat resistance, adhesiveness but also thermal conductivity.

It is another object of the present invention to provide a metal laminate using the polyimide resin and a printed circuit board comprising the same.

To achieve the above object, the present invention provides a polyimide resin formed of a polyimide resin composition comprising a first diamine having at least one ester group, and having a thermal conductivity of 0.22 W / mk or more.

Here, the first diamine may be a compound represented by the following general 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.

On the other hand, the polyimide resin composition comprises a second diamine; Aromatic tetracarboxylic dianhydrides; Organic solvent; And an inorganic filler.

Here, the second diamine may be at least one selected from the group consisting of compounds represented by the following formulas (2) and (3).

(2)

(3)

In the above Formulas 2 and 3,

,

,

,

,

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 mixing ratio of the first diamine to the second diamine may be 3: 7 to 7: 3, based on the total molar amount of the first diamine and the second diamine.

The ratio (a: b) of the total molar number (a) of the first diamine and the second diamine to the molar number (b) of the aromatic aromatic tetracarboxylic dianhydride may be 1 to 1.05: 1.

The polyimide resin of the present invention may exhibit an adhesive strength of 1.1 kgf / cm or more in the adhesive strength evaluation according to the ASTM D2861 standard after being left at a temperature of 121 ° C and a pressure of 2 atm for 10 hours.

According to another aspect of the present invention, there is provided a semiconductor device comprising: a first metal layer; A resin layer provided on the first metal layer; And a second metal layer provided on the resin layer, wherein the resin layer comprises the polyimide resin.

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

Since the polyimide resin of the present invention has a high thermal conductivity of 0.22 W / mk or more and is therefore applied to an insulating layer of a printed circuit board, the polyimide resin of the present invention is superior in heat dissipation to a printed circuit board Can be provided.

Hereinafter, the present invention will be described.

1. Polyimide resin

The present invention provides a polyimide resin having excellent thermal conductivity. The polyimide resin is formed of a polyimide resin composition composed of a specific component, which will be described in detail as follows.

The polyimide resin composition used for forming the polyimide resin of the present invention comprises a first diamine having at least one ester group. The first diamine is not particularly limited as long as it is a diamine having at least one ester group, but it is preferably a compound represented by the following formula (1) (first aromatic diamine).

[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.

The compound represented by Formula 1 is not particularly limited, but 4-aminophenyl-4-aminobenzoate (APAB) is preferable.

Since such a first diamine has an ester group as a crystalline structure, the present invention can provide a polyimide resin having a high thermal conductivity even when a polyimide resin is formed with a polyimide resin composition not containing (mixed) an inorganic filler.

That is, the polyimide resin tends to have a higher thermal conductivity than the epoxy resin, but in order to obtain a polyimide resin exhibiting a required thermal conductivity because of its semi-crystallinity, a polyimide resin composition in which an inorganic filler is mixed should be used .

However, the present invention can form a polyimide resin with a polyimide resin composition containing a first diamine having an ester group, which is a crystalline structure, to obtain a highly crystalline polyimide resin. Therefore, the polyimide resin composition It is possible to provide a polyimide resin exhibiting a thermal conductivity as required even without using a polyimide resin.

On the other hand, the polyimide resin composition of the present invention comprises a second diamine; Aromatic tetracarboxylic dianhydrides; And an organic solvent.

The second 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 (2) and (3) (second aromatic diamine). The use of the compounds represented by the following formulas (2) and / or (3) can increase the dispersibility or solubility with an organic solvent, thereby facilitating the production of a polyimide resin film. That is, the second diamine is preferably a compound having an amorphous structure capable of imparting flexibility to the polyimide resin.

(2)

(3)

In the above Formulas 2 and 3,

,

,

,

,

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 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 (1, 3-bis (4-aminophenoxy) benzene, TPE-R)

The polyimide resin composition of the present invention comprises the first diamine and the second diamine. In this case, the mixing ratio of the first diamine and the second diamine is not particularly limited, but the molar ratio of the first diamine to the second diamine , Preferably in a molar ratio of 3: 7 to 7: 3. This is because not only the thermal conductivity of the polyimide resin 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 adhesiveness of the polyimide resin.

The mixing ratio (mixing ratio) of the first diamine and the second diamine to the aromatic tetracarboxylic dianhydride is not particularly limited, but the total molar number (a) of the first diamine and the second diamine (A: b) of the number of moles of the aromatic diamine to the number of moles (b) of the aromatic aromatic tetracarboxylic dianhydride is 1 to 1.05: 1.

The total molar number (c) of the first diamine, the second diamine and the aromatic tetracarboxylic dianhydride (c) (molar number of first diamine + number of moles of second diamine + number of moles of aromatic tetracarboxylic dianhydride (C: a) of the total molar number of the first diamine and the second diamine (a) (molar ratio of the first diamine to the molar ratio of the second diamine) of the first diamine to the second diamine is preferably 1: 0.1 to 0.9, More preferably 0.4 to 0.5.

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 polyimide resin of the present invention formed of such a polyimide resin composition has a thermal conductivity of 0.22 W / mk or more (specifically, 0.22 to 0.35 W / mk) by introducing an ester group as a crystalline structure into the polyimide molecular structure, .

Meanwhile, the polyimide resin composition of the present invention can provide a polyimide resin having an improved thermal conductivity as well as an inorganic filler. The inorganic filler may be at least one selected from the group consisting of aluminum oxide, boron nitride, aluminum nitride, silica, titanium dioxide and mica, as long as it is well known in the art.

When the polyimide resin composition of the present invention contains an inorganic filler, the content of each component is not particularly limited, but the content of the first diamine is from 1.5 to 3% by weight based on the total weight% of the composition; 1.5 to 5.5 wt% of a second diamine; 5 to 7% by weight of an aromatic tetracarboxylic dianhydride; 40 to 50% by weight of an inorganic filler; And 40 to 50% by weight of an organic solvent.

The polyimide resin of the present invention formed of the polyimide resin composition containing the inorganic filler as described above can exhibit thermal conductivity of 7 W / mk or more. In addition, the polyimide resin of the present invention is allowed to stand at a temperature of 121 캜 and a pressure of 2 atm for 10 hours, and can exhibit an adhesive strength of 1.1 kgf / cm or more when evaluating the adhesive strength according to ASTM D2861.

2. Metal The laminate

The present invention provides a semiconductor device comprising: a first metal layer; A resin layer provided on the first metal layer; And a second metal layer provided on the resin layer.

The first metal layer and the second metal layer included in the metal laminate of the present invention may be a layer on which a circuit pattern is formed or a layer which functions as a heat dissipating layer. The material constituting the first metal layer and the second metal layer is not particularly limited, but is preferably copper, tin, gold or silver. At this time, the first metal layer and the second metal layer may be made of the same or different materials.

The resin layer included in the metal laminate of the present invention is provided between the first metal layer and the second metal layer and is made of the polyimide resin described above. Since the resin layer is made of the polyimide resin, the resin layer is excellent in adhesion to the first metal layer and the second metal layer, and the insulation, heat resistance, and heat radiation of the metal laminate can be enhanced.

3. Printed Circuit Board

The present invention provides a printed circuit board comprising the above-described metal laminate. Specifically, a printed circuit board on which a circuit pattern is formed on the first metal layer and / or the second metal layer included in the metal laminate is provided. 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 made of the polyimide resin as described above, it is excellent in heat dissipation properties as well as physical properties such as insulation and heat resistance.

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 5 and Comparative Example  One]

In Examples 1 to 5, a substrate was coated with a polyimide resin composition having the composition shown in Table 1 below, and dried at 200 占 폚 for about 1 hour to form polyimide resin films each having a thickness of 100 占 퐉.

In Comparative Example 1, an epoxy resin composition having the composition shown in Table 1 below was coated on a substrate and dried at 150 DEG C for about 1 hour to form an epoxy resin film having a thickness of 100 mu m.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Epoxy resin 1
(Kukdo Chemical, YD-011) - - - - - 5.5 g Epoxy resin 2
(Kukdo Chemical, YD-019) - - - - - 8.2 g Epoxy resin 3
(DOW, DER-383) - - - - - 4.9 g Hardener
(EMomentive, DICY) - - - - - 1.4 g Diamine BAPP 3.50 g 4.10 g 4.70 g 5.20 g 2.90 g - 0.26 mol 0.31 mol 0.36 mol 0.41 mol 0.21 mol - APBN 2.50 g 2.90 g 3.20 g 3.70 g 2.00 g - 0.26 mol 0.31 mol 0.36 mol 0.41 mol 0.21 mol - APAB 3.80 g 2.90 g 2.20 g 1.40 g 4.60 g - 0.50 mol 0.40 mol 0.30 mol 0.20 mol 0.60 mol - Aromatic tetracarboxylic dianhydride ODPA 8.10 g 8.00 g 7.80 g 7.70 g 8.30 g - 0.80 mol 0.80 mol 0.80 mol 0.80 mol 0.80 mol - BTDA 2.10 g 2.10 g 2.10 g 2.00 g 2.20 g - 0.20 mol 0.20 mol 0.20 mol 0.20 mol 0.20 mol - NMP 80 ml 80 ml 80 ml 80 ml 80 ml 80 ml

[ Experimental Example  1] Thermal conductivity evaluation

The thermal conductivities of the resin films obtained in Examples 1 to 5 and Comparative Example 1 were evaluated according to ASTM D5470 standard, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Thermal conductivity (W / mk) 0.31 0.26 0.25 0.22 0.33 0.2

As shown in Table 2, it was confirmed that the polyimide resins of Examples 1 to 5 had a thermal conductivity of 0.22 W / mk or more, which was higher than that of Comparative Example 1.

[ Example  6 to 10 and Comparative Example  2]

Compositions for forming an insulating layer were prepared by mixing inorganic fillers in the resin compositions of Examples 1 to 5 and Comparative Example 1, respectively. At this time, the mixing ratio (weight ratio) of the resin composition to the inorganic filler was 20:80, and specific compositional ratios and components are shown in Table 3 below.

Example 6
(Example 1) Example 7
(Example 2) Example 8
(Example 3) Example 9
(Example 4) Example 10
(Example 5) Comparative Example 2
(Comparative Example 1) Table 1
Polyimide
Resin composition 20 g 20 g 20 g 20 g 20 g 20 g Inorganic filler rectangle
Filler 1
(Sumotomo, AA-3) 20 g 20 g 20 g 20 g 20 g 20 g rectangle
Filler 2
(Momentive, PT390) 60 g 60 g 60 g 60 g 60 g 60 g

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

After coating each of the compositions of Examples 6 to 10 and Comparative Example 2 to a thickness of 100 占 퐉 in a copper foil having a thickness of 35 占 퐉, the compositions of Examples 6 to 10 at 200 占 폚 and the composition of Comparative Example 2 at 150 占 폚 And dried for 1 hour to form a resin layer, respectively. 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  2] metal The laminate  Property evaluation

Physical properties of the metal laminate prepared in Preparation Examples 1 to 5 and Comparative Preparation Example 1 were evaluated by the following methods. The results are shown in Table 4 below.

1. Coating property: The difference between the thickness of the composition applied on the copper foil and the thickness of the resin layer formed on the copper foil was measured and evaluated (?: Thickness deviation 占 占 퐉,?: Thickness variation 占 占 퐉,?: ± 4 μm, ×: thickness deviation ± 5 μm).

2. Thermal conductivity: ASTM D5470 standard.

3. Heat resistance: The time for blistering was measured after floating on 288 ° C water bath.

4. Moisture resistance: After standing for 24 hours in an environment of 85% humidity and 85 ° C temperature, it was evaluated according to ASTM D2861 standard.

5. Adhesive strength: After standing for 10 hours at a temperature of 121 占 폚 and a pressure of 2 atm, it was evaluated according to ASTM D2861 standard.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Comparative Preparation Example 1 Coating property ◎ ◎ ◎ ◎ ○ ◎ Thermal conductivity (W / mK) 10 9 8 8 10 6 Heat Resistance (S / D @ 288) > 10 min > 10 min > 10 min > 10 min > 10 min > 10 min Moisture resistance (@ 1 oz-kgf / cm) 1.2 1.1 1.1 1.1 1.2 0.9 Adhesion (@ 1 Oz-kgf / cm) 1.5 1.4 1.5 1.5 1.5 1.5

Referring to Table 4, it can be confirmed that the metal laminate of Production Examples 1 to 5 of the present invention is superior in physical properties to Comparative Production Example 1. In particular, it can be confirmed from the results of the moisture resistance evaluation that the metal laminate of the present invention has excellent thermal conductivity and maintains excellent adhesive strength even when used for a long time.

Claims (10)

And a first diamine having at least one ester group,
Polyimide resin having a thermal conductivity of 0.22 W / mk or more. The method according to claim 1,
Wherein the first diamine is 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. The method according to claim 1,
Wherein the polyimide resin composition comprises a second diamine; Aromatic tetracarboxylic dianhydrides; And a polyimide resin further comprising an organic solvent. The method of claim 3,
And the second diamine is at least one selected from the group consisting of compounds represented by the following general formulas (2) and (3).
(2)

(3)

In the above Formulas 2 and 3,
A and B are the same or different from each other, and each independently,

,

,

,

,

And

As shown in FIG. The method of claim 3,
Wherein a mixing ratio of the first diamine and the second diamine is 3: 7 to 7: 3, based on the total molar amount of the first diamine and the second diamine. The method of claim 3,
Wherein the ratio (a: b) of the total molar number (a) of the first diamine and the second diamine to the molar number (b) of the aromatic aromatic tetracarboxylic dianhydride is 1 to 1.05: 1. The method of claim 3,
Wherein the polyimide resin composition further comprises an inorganic filler. 8. The method of claim 7,
A polyimide resin exhibiting an adhesive strength of 1.1 kgf / cm or more in an 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. A first metal layer;
A resin layer provided on the first metal layer; And
And a second metal layer provided on the resin layer,
Wherein the resin layer comprises the polyimide resin according to any one of claims 1 to 8. A printed circuit board comprising the metal laminate of claim 9.