KR101401657B1 - Polyimide resin composition and metal clad laminate the same - Google Patents

Abstract

The present invention relates to a polyimide resin composition and a metal laminate using the same, and more particularly, to a metal laminate comprising a metal foil and a polyimide layer laminated on two or more surfaces of the metal foil, Which is excellent in adhesion and adhesion to a polyimide layer. More specifically, the present invention relates to a polyimide resin composition containing a foam inhibiting additive having a specific structure and a metal laminate using the same.

Polyimide, an anti-foaming additive, a metal laminate

Description

TECHNICAL FIELD The present invention relates to a polyimide resin composition and a metal laminate using the same,

The present invention relates to a polyimide resin composition and a metal laminate using the same, and more particularly, to a metal laminate comprising a metal foil and a polyimide layer laminated on two or more surfaces of the metal foil, The present invention relates to a polyimide resin composition and a metal laminate using the same.

[0003] As miniaturization, multifunctionalization, and thinning of electronic devices have been made, circuit boards used in electronic devices are required to be further densified. In order to meet such demands, a method of multilayering circuit boards has been used. In addition, a flexible printed circuit board in which a flexible circuit board is provided to allow a circuit board to be installed in a narrow space may be used, or a circuit having a narrow line width may be used in order to obtain a large number of circuits in the same space.

Soldering as a method for multilayering a circuit board has a problem of causing environmental problems. Accordingly, there is a demand for an adhesive having high adhesive strength, high heat resistance and low moisture absorption rate for multilayering of circuit boards. However, a metal laminate plate in which a conventional acrylic or epoxy adhesive is used to adhere a polyimide film to a metal foil is insufficient for a circuit board requiring multilayering, flexibility, high adhesive strength, and high heat resistance. Accordingly, a flexible metal laminate of a non-adhesive type 2-layered copper clad laminate (2CCL) in which a polyimide layer and a metal foil are directly bonded without using an adhesive has been developed. Such a metal laminate is a flexible circuit board material having excellent thermal stability, durability and electrical characteristics compared to 3-layer laminate (3CCL) in which a metal layer and a polyimide layer are bonded using a conventional adhesive.

Meanwhile, the metal of the conductive metal foil in the present invention means a conductive metal such as copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, or an alloy thereof. Generally, copper is used extensively but is not necessarily limited thereto.

The metal laminate has a cross-section metal laminate composed of a metal foil and a polyimide layer and a double-side metal laminate in which a polyimide layer is present between two metal foils.

There is often a problem of foaming at the interface between the polyimide layer and the polyimide layer in a manufacturing process such as coating, curing, drying, lamination for producing a double-sided metal laminate in the production of the metal laminate.

In general, foaming is a byproduct, which is generated during the heat treatment at a high temperature to obtain polyamic acid in the final polyimide form, so that the polyamic acid and the hydrogen-bonded solvent evaporate to form the polyimide layer at the interface . Such a foaming problem can be suppressed when the heat treatment is carried out at a low temperature for a long time or when the drying is long at 100 to 220 ° C. However, The foaming phenomenon often occurs because the residence time at a lower temperature is short. Particularly, if the operation speed is increased to increase the productivity, the residence time at the low temperature becomes shorter and the foaming phenomenon is more likely to occur.

The present invention provides a metal laminate comprising a metal foil and a polyimide layer laminated on two or more surfaces of the metal foil, wherein at least one layer selected from the remaining layers except the layer in contact with the metal foil of the polyimide layer And an object of the present invention is to provide a metal laminate made of a polyimide resin composition containing an additive for suppressing the foaming phenomenon occurring at the interface between polyimide layers.

More specifically, the present invention relates to a method of coating a polyimide resin composition comprising a imidazole-triazine or bismaleimide foam inhibiting additive having a specific structure on at least one layer selected from the remaining layers except for the layer in contact with the metal foil , And to prevent the foaming phenomenon occurring at the interface between the polyimide layers by producing a metal laminate through roll-to-roll curing.

The present invention provides a metal laminate comprising a metal foil and a polyimide layer laminated on at least one surface of the metal foil, wherein the foaming phenomenon occurring at the interface between the polyimide layers is suppressed A polyimide resin composition excellent in adhesion and adhesion to a polyimide layer, and a metal laminate using the same.

Hereinafter, the present invention will be described in more detail.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, wherein like reference numerals refer to like elements throughout. And a description of the known function and configuration will be omitted.

The present invention relates to a polyimide resin composition and a metal laminate using the same. In the present invention, a polyimide resin is a generic term of a resin having an imide ring structure, and examples thereof include polyimide, polyamideimide, polyesterimide But is not limited thereto.

More specifically, the present invention provides a polyimide resin composition comprising an anti-foaming additive represented by the following formula (1) or (2) having a specific structure.

The present invention also provides a metal laminate comprising a metal foil and a polyimide layer laminated on at least one surface of the metal foil, wherein at least one layer selected from the remaining layers except the layer in contact with the metal foil of the polyimide layer By providing the polyimide resin composition, the foaming phenomenon that may occur at the interface between the polyimide layers at the time of curing is suppressed, and a metal laminate having excellent appearance can be provided.

In the present invention, the polyimide resin composition is characterized by containing a foam inhibiting additive represented by the following general formula (1) or (2).

[Chemical Formula 1]

Wherein X is a chemical bond, C1-C10 alkylene or C2-C10 alkenylene; R ₁ to R ₅ independently of one another are hydrogen, halogen, C ₁ to C 10 alkyl, C 2 to C 10 alkenyl, amino or C 6 to C 10 aryl.

(2)

이고; 상기 Z는 Y의 정의와 동일하며; R₁₁ 내지 R₁₈은 서로 독립적으로 수소, 할로겐, C1 ~ C10의 알킬, C2 ~ C10의 알케닐 또는 C6 ~ C10의 아릴이다.][In the formula 2, Y is a chemical bond or a _{-S-, -O-, -CONH-, -SO 2} -, -CO-, -C (CH 3) 2 -, -C (CF 3) 2 - or

ego; Z is the same as defined for Y; R ₁₁ to R ₁₈ independently of one another are hydrogen, halogen, C 1 to C 10 alkyl, C 2 to C 10 alkenyl or C 6 to C 10 aryl.

Examples of the additive for suppressing foaming represented by the above-mentioned formula (1) include imidazole-triazine-based additives such as 2,4-diamino-6- [2- (2-methyl-1- imidazolyl) ethyl] (2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] (2,4-diamino-6- [2- (2-undecyl-1-imidazolyl) ethyl] -s-triazine) and the like.

The anti-foaming additive represented by the above-mentioned general formula (2) is a bismaleimide-based compound, and specific examples thereof include N, N '- (2,2'-dimethyl-1,1'-biphenyl-4,4'- (2,2'-dimethyl-1,1'-biphenyl-4,4'-diyl) bismaleimide), N, N '- (4,4'-diphenylmethane) bis Maleimide (N, N '- (4,4'-diphenylmethane) bismaleimide), bis (3-ethyl-5-methyl-4-maleimidophenyl ) methane), but are not limited thereto.

In the present invention, it is possible to produce a metal laminate in which the foaming inhibiting additive is excellent in adhesion and adhesion to the polyimide layer and suppresses the foaming phenomenon occurring at the interface between the polyimide layers. The present invention has been completed.

Particularly, the imidazole-triazine-based additive represented by the above formula (1) is very effective for improving the adhesion with the polyimide layer and the adhesion, and has an excellent effect in suppressing the foaming phenomenon occurring at the interface between the polyimide layers

In the present invention, the foam inhibiting additive is preferably added in an amount of 1 to 10% by weight based on the total weight of the polyimide resin composition. When the addition amount of the foaming inhibiting additive is within the above range, the effect of improving the adhesion between the polyimide layers increases as the addition amount is increased. However, when the amount exceeds the above range, the degree of increase of the adhesion strength is very small, and the mechanical strength and heat resistance May be lowered.

In the present invention, the polyimide resin composition comprises an aromatic diamine and an aromatic dianhydride as known in the art, and the aromatic diamine is selected from the group consisting of p-phenylenediamine, m-phenylene diamine, 3 '-Methoxy-4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, diaminotoluene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, benzidine , Diaminodiphenylsulfone, diaminonaphthalene, and the like are preferably used, but not limited thereto.

The aromatic dianhydride may be at least one selected from pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetracarboxylic dianhydride (4,4'- (4,4'-isopropylbiphenoxy) biphthalic anhydride), 2,2'-bis- (3 , 4-dicarboxyphenyl) hexafluoropropane dianhydride, ethylene glycol bis (anhydro-trimellitate), and the like, but is not limited thereto.

The aromatic dianhydride and the aromatic diamine are preferably added in a molar ratio of 1: 0.95 to 1.05, and when the molar ratio is out of the range, the viscosity after the polymerization is lowered and the post-process becomes difficult.

Hereinafter, a method of producing the polyimide resin composition according to the present invention will be described.

The polyimide resin composition according to the present invention can be produced by adding an organic solvent to a reaction vessel and adding an aromatic diamine, an anti-foaming additive and an aromatic dianhydride to the reaction mixture. When the imidazole-triazine-based additive is used as the foam inhibiting additive, the aromatic diamine, the imidazole-triazine additive and the aromatic dianhydride are sequentially charged in this order, and when the bismaleimide-based additive is used First, an aromatic diamine, aromatic dianhydride is first polymerized, and then a bismaleimide-based additive is added. This is because, when the bismaleimide-based additive is added before the aromatic dianhydride, it reacts with the aromatic diamine and solidifies.

The organic solvent usable in the present invention is not particularly limited and may be any organic solvent known in the art. For example, N-methylpyrrolidone (NMP), N, N'-dimethylacetamide (DMAc) But are not limited to, polar solvents such as tetrahydrofuran (THF), N, N'-dimethylformamide (DMF), dimethylsulfoxide (DMSO), cyclohexane and acetonitrile.

The amount of the organic solvent may be an amount sufficient to uniformly dissolve each component, and it is preferable that the solids content of the solvent contains 10 to 20% by weight. When the solute content is less than 10% by weight, the viscosity of the solution becomes too high to uniformly apply the coating. When the solute content exceeds 20% by weight, the use of an unnecessary solvent is increased.

In the polymerization reaction of the present invention, the aromatic diamine, the foaming inhibiting additive and the aromatic dianhydride are dissolved in the presence of a polar solvent, and the reaction is carried out under ordinary condensation reaction conditions to obtain the polyimide resin composition of the present invention. The condensation reaction is preferably carried out in a nitrogen atmosphere, and may be carried out at an ambient temperature or by increasing the temperature as necessary in order to accelerate the reaction rate.

In the present invention, a small amount of aromatic diamine or aromatic dianhydride other than the above-mentioned compounds may be added to the polyimide resin composition for forming the polyimide layer. In order to facilitate application or curing of the polyimide resin composition or to improve other physical properties, additives such as a defoaming agent, an anti-gel agent, and a curing accelerator may be further added.

The present invention also provides a metal laminate comprising a metal foil and a polyimide layer laminated on at least one surface of the metal foil, wherein at least one layer selected from the remaining layers except the layer in contact with the metal foil of the polyimide layer, And a polyimide resin composition according to the present invention.

In the present invention, even a polyimide layer having the same composition can be formed in multiple layers by repeating the process of coating and drying it a plurality of times and then curing it all at once.

In the present invention, the polyimide layer is formed by adding a polyimide resin composition obtained by adding and mixing an aromatic diamine, an anti-foaming additive (imidazole-triazine or bismaleimide-based) and an aromatic dianhydride to an organic solvent, By coating one or more times on at least one layer selected from the remaining layers except for the layer in contact with the substrate, and then curing it.

Therefore, the polyimide resin composition according to the present invention is coated on the remaining polyimide layer except for the layer in contact with the metal foil. The coating method known in the art can be used for coating, and for example, a die coater, A comma coater, a reverse comma coater, a gravure coater, or the like can be used. The polyimide resin composition coated on the metal foil may be dried at a temperature lower than the boiling point of the solvent, typically about 100 to 300 ° C, more preferably about 150 to 250 ° C, although it depends on the structure and conditions of the oven have.

After the polyimide resin composition according to the present invention is coated and dried on the polyimide layer laminated on one or both surfaces of the metal foil as described above, the polyimide resin composition is heated to a temperature of preferably 400 ° C, A polyimide layer containing an anti-foaming additive can be formed. The curing may be carried out by gradually heating in an oven under a nitrogen atmosphere or a vacuum, or by continuously passing a high temperature through a nitrogen atmosphere.

1, the polyimide resin composition according to the present invention is used for the remaining layers except the layer in contact with the metal foil. As shown in FIG. 1, The present invention is not limited thereto.

In the present invention, the metal foil material may preferably be selected from copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten or alloys thereof.

As described above, according to the present invention, at least one layer selected from the metal foil and the other layers except for the layer in contact with the metal foil of the polyimide layer stacked on two or more surfaces thereof on one or both surfaces thereof is a polyimide resin composition according to the present invention The foaming phenomenon occurring at the interface between the polyimide layers is minimized, and a metal laminate for an excellent flexible printed circuit board can be produced.

In the present invention, a polyimide resin composition comprising a metal foil and an anti-foaming additive having a specific structure on at least one layer selected from the rest of the polyimide layers stacked on two or more sides of the metal foil, It is possible to provide a metal laminate for a printed circuit board capable of solving the problem of foaming between polyimide layers.

Hereinafter, the present invention will be better understood by reference to the following examples, and the following examples are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

The monomers and solvents used in Examples and Comparative Examples are as follows.

DMIT: 2,4-Diamino-6- [2- (2-methyl-1-imidazolyl) ethyl]

DUIT: 2,4-Diamino-6- [2- (2-undecyl-1-imidazolyl) ethyl]

NBM: N, N '- (2,2'-dimethyl-1,1'-biphenyl-4,4'-diyl) bismaleimide

NDB: N, N '- (4,4'-diphenylmethane) bismaleimide

BMM: bis (3-ethyl-5-methyl-4-maleimidophenyl) methane

ODA: 4.4'-diaminodiphenyl ether

PDA: p-phenylenediamine

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

DMAc: N, N-dimethylacetamide

[Test Example]

1) degree of foaming

Record 5 averages of the number of foams generated within 10 cm x 10 cm. If there is no foaming, it is recorded as 'None'. If it is impossible to measure due to foaming on the front side, it is recorded as 'completely separated from the floor'.

[Synthesis Examples A to G]

The following Table 1 shows the composition ratios of the polyimide resin composition of the present invention. The solubility of the aromatic diamine and the aromatic dianhydride in a molar ratio of 1.01: 1 was determined by solubility (relative to the solvent of N, N-dimethylacetamide (DMAc) solid contents) were added in an amount of 13% by weight, additives for inhibiting foaming were added as shown in Table 1 below, and reacted for 6 hours at room temperature under nitrogen atmosphere to prepare the polyimide resin compositions of Synthesis Examples A to G.

[Table 1]

[Example 1]

A polyimide resin composition G was coated on an ED copper foil having a thickness of 12 占 퐉 and dried at 140 占 폚 for 10 minutes to form a polyimide layer (1 ^st ). Then, after this tangent applying a polyimide-based resin composition B on the polyimide layer (1 ^st) and dried at 140 ℃ 20 minutes to form a polyimide layer (2 ^nd). Thereafter, the film was cured by raising the temperature from room temperature to 380 ° C at a heating rate of 2 m / min in a roll to roll IR curing machine. The thickness of the polyimide layer (1 ^st ) after curing was 3 μm and the thickness of the polyimide layer 2 ^nd ) were 10, 20, 30 and 40 ㎛, respectively. The physical properties thereof are shown in Table 2 below.

[Example 2]

A metal laminate was produced in the same manner as in Example 1, except that C was used in place of the polyimide resin composition B used in Example 1. A metal laminate having a polyimide layer (1 ^st ) having a thickness of 3 μm and a polyimide layer (2 ^nd ) having thicknesses of 10, 20, 30 and 40 μm was prepared, and the physical properties thereof are shown in Table 2 .

[Example 3]

A metal laminate was prepared in the same manner as in Example 1, except that D was used instead of the polyimide resin composition B used in Example 1. A metal laminate having a polyimide layer (1 ^st ) having a thickness of 3 μm and a polyimide layer (2 ^nd ) having thicknesses of 10, 20, 30 and 40 μm was prepared, and the physical properties thereof are shown in Table 2 .

[Example 4]

A metal laminate was produced in the same manner as in Example 1, except that E was used in place of the polyimide resin composition B used in Example 1. A metal laminate having a polyimide layer (1 ^st ) having a thickness of 3 μm and a polyimide layer (2 ^nd ) having thicknesses of 10, 20, 30 and 40 μm was prepared, and the physical properties thereof are shown in Table 2 .

[Example 5]

A metal laminate was produced in the same manner as in Example 1, except that F was used in place of the polyimide resin composition B used in Example 1. A metal laminate having a thickness of polyimide layer (1 ^st ) of 3 탆 and a thickness of polyimide layer (2 ^nd ) of 10, 20, 30 and 40 탆, respectively, was prepared, .

[Comparative Example 1]

A metal laminate was prepared in the same manner as in Example 1 except that A was used instead of the polyimide resin composition B used in Example 1. A metal laminate having a polyimide layer (1 ^st ) having a thickness of 3 μm and a polyimide layer (2 ^nd ) having thicknesses of 10, 20, 30 and 40 μm was prepared, and the physical properties thereof are shown in Table 2 .

[Table 2]

As can be seen in Table 2, the metal foil and in its side or comprising a polyimide layer which is laminated two or more layers on a double-sided metal laminate, the additive for foaming suppressed according to the present invention the 2 ^nd layer of said polyimide layer It was confirmed that the foaming was remarkably improved as compared with Comparative Example 1 in which the additive was not used.

1 is a cross-sectional view illustrating a structure of a metal laminate according to a preferred embodiment of the present invention.

DESCRIPTION OF THE RELATED ART [0002]

A: Metal foil

B: Polyimide layer (1 ^st )

C: A polyimide layer (2 ^nd ) containing an ^anti-

Claims (5)

A polyimide resin composition comprising an anti-foaming additive represented by the following formula (1). [Chemical Formula 1]

Wherein X is a chemical bond, C1-C10 alkylene or C2-C10 alkenylene; R ₁ to R ₅ independently of one another are hydrogen, halogen, C ₁ to C 10 alkyl, C 2 to C 10 alkenyl, amino or C 6 to C 10 aryl. The method according to claim 1, Wherein the foam inhibiting additive is added in an amount of 1 to 10% by weight based on the total weight of the polyimide resin composition. A metal laminate comprising a metal foil and a polyimide layer laminated on at least one surface or both surfaces thereof, Wherein at least one layer selected from the remaining layers except the layer in contact with the metal foil in the polyimide layer comprises an anti-foaming additive represented by the following formula (1), wherein the polyimide layer is cured in a roll- sieve. [Chemical Formula 1]

Wherein X is a chemical bond, C1-C10 alkylene or C2-C10 alkenylene; R ₁ to R ₅ independently of one another are hydrogen, halogen, C ₁ to C 10 alkyl, C 2 to C 10 alkenyl, amino or C 6 to C 10 aryl. The method of claim 3, Wherein the polyimide layer is laminated to a thickness of 1 to 50 占 퐉. 5. The method of claim 4, Wherein the metal foil is selected from copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, or an alloy thereof.

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