TWI603839B - Flexible metal clad laminate - Google Patents

Description

Flexible metal clad laminate

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a flexible metal clad laminate for use in the manufacture of flexible printed circuit boards, which is characterized in that it does not cause curling of the product, adhesion strength with a metal cladding is advantageous, and dimensions after heat treatment. The change is small, especially after absorbing moisture, it has excellent resistance to solder.

The flexible metal clad laminate for manufacturing a flexible printed circuit board is a laminate of a conductive metal clad and an insulating resin, which can be subjected to fine circuit processing and can be bent in a narrow space, As the size and weight of electronic devices continue to decrease, the use of such laminates continues to increase. The flexible metal clad laminate is divided into two layers and three layers. The three layers using the adhesive have the following problems compared to the two layers: heat resistance and flame retardancy are low and will be used in the heat treatment process. There are large dimensional changes. Therefore, the current driving force in the manufacture of flexible printed circuit boards is generally to use a two-layer, rather than three-layer, flexible metal clad laminate.

The use of double-sided metal clad laminates continues to increase, depending on the current drive for the slenderness, weight, length and size of the circuit. The double-sided metal clad laminate is substantially fabricated by stacking a metal foil and a thermoplastic polyimide which is formed on the outermost layer of the insulating layer, but has the following problems: due to the presence of the thermoplastic polyimide resin, After the insulating layer absorbs moisture, the impedance to the solder becomes poor. In particular, the normal soldering temperature is at a level of 200 ° C, but since the lead-free soldering process becomes common and its temperature is 250 ° C or higher, the resistance to solder after absorbing moisture becomes more and more important.

Patent Document 1 on the known art cites the following example: using a polyimine resin having a special structure as a thermoplastic polyimide resin layer, in this example, the heat-resistant temperature after absorbing moisture is just 260 ° C, To the solder under severe conditions of 300 ° C or higher There is a problem with the impedance.

Prior technical literature Patent literature

(Patent Document 1) Japanese Patent Application Publication No. 2002-363284

The present invention relates to a flexible metal clad laminate for manufacturing a printed circuit board and a method of manufacturing the same, which has the object of solving the problems of the prior art by providing a flexible metal cladding The laminate has excellent resistance to solder at 300 ° C or higher after absorbing moisture, it does not cause curling of the product, its bond strength with copper foil is high, and it is after heat treatment. The dimensional change is small.

The following is the invention for achieving the above object.

In a general aspect, a flexible metal clad laminate is provided, wherein a metal layer is formed on one surface or both surfaces of an insulating layer composed of a plurality of polyimine-based resin layers, and the metal the plurality of polyimide-based resin layer into contact with the layer 1 X 10 ⁸ Pa at 300 deg.] C or higher and having 1 X 10 ⁸ Pa or lower storage modulus at 350 ℃.

The present invention provides a flexible metal clad laminate which has excellent resistance to solder after absorbing moisture, does not cause curling of the product, has high bonding strength with copper foil, and has dimensional change after heat treatment. small.

The present invention provides a flexible metal clad laminate in which a metal layer is formed on one surface or both surfaces of an insulating layer composed of a plurality of polyimine-based resin layers, and the poly layer is in contact with the metal layer. the acyl imine resin layer having a 1 X 10 ⁸ Pa or more and having 1 X 10 ⁸ Pa or less at 350 deg.] C storage modulus at 300 ℃.

Providing a flexible metal clad laminate, wherein the plurality of polyimide groups are The resin layer has a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide-based resin layer laminated in this order.

Further, the polyimine-based resin layer in contact with the metal layer is a thermoplastic polyimide-based resin layer having a glass transition temperature of 300 ° C or lower.

The polyimine-based resin layer in contact with the metal layer measures a linear thermal expansion coefficient of 50 ppm/K or less at a temperature ranging from 100 ° C to 200 ° C.

Further, in the flexible metal clad laminate produced by the polyimine-based resin layer according to the present invention, it is absorbed after being treated at 40 ° C and 90% relative humidity for 72 hours. The resistance temperature to the solder after the gas is 300 ° C or higher.

Moreover, the present invention provides the flexible metal clad laminate, wherein the polyimine-based resin layer in contact with the metal layer contains 50 to 100 mol% of the following [Chemical Formula 1] Structural units.

The -X- contained in [Chemical Formula 1] is an aromatic diamine compound containing one or two or more selected from the following structures and which can be used singly or by copolymerization.

-X ₁ - is selected from the group consisting of -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -CONH-, -C(CF ₃ ) ₂ -, -(CH ₂ ) - or a combination thereof.

Included in [Chemical Formula 1] It is a dianhydride which contains one or two or more selected from the following structures and can be used singly or by copolymerization.

Hereinafter, the constitution of the present invention will be described in detail.

The present invention provides a flexible metal clad laminate having a multilayer structure in which a metal clad layer is formed on one surface or both surfaces of an insulating layer, which is composed of a plurality of polyimine-based resins. .

The polyimine-based resin layer has a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide-based resin layer laminated in this order.

The flexible metal clad laminate can be produced by forming a single polyimide-based resin layer onto a metal clad layer, but in this case, there are the following problems. First, when a thermosetting polyimine-based resin layer is used alone, the adhesion strength to the metal foil is low, and since the thermoplastic polyimide-based resin layer is not provided, it is impossible to manufacture a double-sided flexible type. The thermal lamination process of the metal cladding has the problem of curling of the product before and after etching. In contrast, in the case of using a thermoplastic polyimide-based resin layer alone, since the linear thermal expansion coefficient of the insulating layer is high, the dimensional change after heat treatment is large, and there is a problem that the product is curled before and after the etching. . Therefore, the insulating layer constituting the flexible metal clad laminate of the present invention has a multilayer structure composed of a thermoplastic polyimide-based resin layer, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide. The resin layer of the resin layer is composed of a plurality of polyimine-based resin layers.

The resin layer of the thermoplastic resin layer Juxi Juxi imine of the present invention and the metal layer in contact with representatives of the imine and having at 300 ℃ 1 X 10 ⁸ Pa or more and X 10 ⁸ at 1 at 350 ℃ The characteristics of Pa or lower storage modulus.

Specifically, it is preferably 1 X 10 ⁸ Pa or higher and 1 X 10 ¹⁰ Pa or lower storage modulus at 300 ° C and 1 X 10 ⁸ Pa or lower and 1 X at 350 ° C. 10 ⁵ Pa or higher storage modulus.

In the case where the storage modulus is lower than 1 X 10 ⁸ Pa at 300 ° C, there is a problem that it is difficult to resist the solder after absorbing moisture, and the material brittleness increases in the case where the storage modulus is more than 1 X 10 ¹⁰ Pa. And the problem of reduced bending characteristics. Further, in the case where the storage modulus is more than 1 × 10 ⁸ Pa at 350 ° C, there is a problem of insufficient thermoplasticity. In the case where the storage modulus is less than 1 × 10 ⁵ Pa, since the resin melts and flows, it is difficult to carry out heat. The problem of the lamination process.

Further, the thermoplastic polyimide-based resin layer according to the present invention may have a glass transition temperature of 300 ° C or lower. More specifically, the glass transition temperature is between 200 and 300 °C.

In the case where the thermoplastic polyimide-based resin layer does not satisfy the above conditions, for example, if the glass transition temperature is not higher than 300 ° C and the storage modulus measured at 350 ° C is higher than 1 X 10 ⁸ Pa, then It is advantageous for the resistance of the solder after absorbing moisture, but the fluidity of the resin is insufficient at a high temperature, so that there is a possibility that the thermal lamination process cannot be performed and bonding with another substrate such as a cap layer and a prepreg. The problem of low strength. In view of the foregoing problems, the thermoplastic polyimine-based resin layer constituting the present invention has a glass transition temperature of 300 ° C or less and a storage modulus of 1 × 10 ⁸ Pa or less at 350 ° C.

If the water-absorbing polyimine resin is immersed in a solder bath at a high temperature, the absorbed moisture will rapidly evaporate and between the polyimide layer or the polyimide layer and the metal. Defects such as layer separation and defects such as foaming and swelling occur in the resin layer at the interface between the cladding layers. If the polyimide resin is immersed in a high-temperature solder bath, the water vapor absorbed in the resin layer will evaporate rapidly. At this time, it seems that only the polyimide resin has a storage mold capable of withstanding the water vapor pressure of moisture. In the case of a digital level, defects that occur when immersed in the solder bath can be avoided. The present inventors have conducted research based on this point of view, and concluded that the storage modulus measured at 300 ° C should be 10 ⁸ Pa or more to absorb moisture 72 at 40 ° C and 90% relative humidity. After an hour or more, there is an impedance to 300 ° C of solder after absorbing moisture, and via this characteristic, a flexible metal clad laminate having a particularly excellent resistance to solder after absorbing moisture can be manufactured.

Further, the thermoplastic polyimide-based resin layer in contact with the metal layer has a linear thermal expansion coefficient of 50 ppm/K or less measured between 100 ° C and 200 ° C.

More specifically, the coefficient of linear thermal expansion is preferably between 17 and 50 ppm/K.

The linear thermal expansion coefficient of the entire insulating layer should be low to avoid curling of the flexible metal clad laminate after heat treatment and to increase dimensional stability. Since the thermoplastic polyimide-based resin layer has a high coefficient of linear thermal expansion to the thermosetting polyimide-based resin layer, it is important to control the linear thermal expansion coefficient of the thermoplastic polyimide-based resin layer to control the entire insulating layer. Linear thermal expansion coefficient. A thermoplastic polyimide-based resin having a high storage modulus at a relatively high temperature is required to control the linear thermal expansion coefficient of the thermoplastic polyimide-based resin layer. The thermoplastic polyimide-based resin layer of the present invention has a storage modulus of 1 × 10 ⁸ Pa or higher measured at 300 ° C, and is 100 to 200 ° C because the storage modulus is high at a high temperature. The measured linear thermal expansion coefficient is 50 ppm/K or less.

Next, a polyimide-based resin according to the present invention will be explained.

The precursor of the polyimide-based resin used in the present invention is based on organic The solution is obtained by reacting a diamine and a dianhydride. Dissolving or diffusing the diamine as a slurry into the organic solution in an inert environment such as argon or nitrogen, when the diamine is dissolved or diffused in the organic solvent as a slurry or when the diamine is in a solid state, A dianhydride is added.

As long as it can dissolve the polyimine precursor, it is not particularly limited before the synthesis of the polyimine The solvent used to drive the solution. Examples thereof may include an anthraquinone solvent such as dimethyl hydrazine and diethyl hydrazine, a formamide solvent such as N,N-dimethylformamide and N,N-diethylformamide, B. Amidoxime solvent such as N,N-dimethylacetamide and N,N-diethylacetamide, pyrrolidone solvent such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol a solvent such as phenol, o-cresol, m-cresol or p-cresol, xylenol, halogenated phenol and catechol, ether solvent such as diglyme, triglyme, tetraethylene glycol Methyl ether, tetrahydrofuran and dihydroxy acid, alcohol solvent such as methanol, ethanol and butanol, cellosolve such as butyl cellosolve, hexamethylphosphonium, γ-butyrolactone, etc., these examples may preferably be separate Use or use as a mixture, and in turn, aromatic hydrocarbons such as xylene and toluene may be used.

The polycondensate according to the present invention is not particularly limited as long as the dianhydride is a dianhydride. The dianhydride contained in the amine resin layer may, for example, be an aliphatic or cycloaliphatic tetracarboxylic dianhydride such as 2,2'-hexafluoropropylenedibutyric dianhydride, 2,2-di ( 4-hydroxyphenyl)dibenzoate propyl-3,3'4,4'-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5 -(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and bicyclo[2,2,2]-oct-7-one-2, 3,5,6-tetracarboxylic dianhydride; and aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 3,3' 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3'4,4'-dimethyl Diphenyl decane tetracarboxylic dianhydride, 3,3'4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-double Phenol A dianhydride, 3,3'4,4'-perfluoroisopropylidene dicarboxylic acid dianhydride, 3,3'4,4'-diphenyltetracarboxylic dianhydride, bis(decanoic acid) benzene Phosphine dianhydride, p-phenylene-bis(triphenylphosphonate) dianhydride, m-phenylene-bis(triphenylphosphonate) dianhydride, bis(triphenylphosphonic acid)- 4,4'-diphenylether dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and bis(triphenylphosphonic acid)-4,4' diphenylmethane dianhydride .

a diamine contained in a plurality of polyimine-based resin layers according to the present invention Unrestricted and greatly limited, examples thereof may include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Alkane, 4,4'-diaminodiphenyl ether, 4,4'-diaminophenyl sulfide, 4,4'-diaminophenyl fluorene, 1,5-diaminonaphthalene, 3,3-di Methyl-4,4'-diaminodiphenyl, 3,5-diamino-benzoic acid, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydrazine, 6-Amino-1-(4'-aminophenyl)-1,3,3-trimethylhydrazine, 4,4'-diaminobenzamide, 3,5-diamino-3'-three Fluoromethylbenzamide, 3,5-diamino-4'-trifluoromethylbenzamide, 3,4'-diaminodiphenyl ether, 2,7-diaminopurine, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-methylene-bis(2-chloroaniline), 2,2'5,5'-tetrachloro-4,4'-di Aminodiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxydiphenyl, 3,3'-dimethoxy-4,4'-di Aminophenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4-di(4- Aminophenoxy)-diphenyl, 1,3-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)anthracene, 4,4' (p-phenylene) Propylene)diphenylamine, 4,4'(m-phenylene isopropylidene)diphenylamine, 4,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-amino- 2-trifluoromethylphenoxy)phenyl]hexafluoropropane and 4,4'-bis[4-(4-amino-2-trifluoromethyl)phenoxy]-octafluorophenyl; aromatic a diamine such as diaminotetraphenylthiophene having two amino groups bonded to an aromatic ring and a hetero atom of a nitrogen atom other than the amino group; an aliphatic diamine and a cycloaliphatic diamine such as 1,1-m-phenylene Dimethylamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethyldiamine, ninethylenediamine, 4,4-diaminoheptane methylenediamine, 1 , 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiethylenediamine, hexahydro-4,7-bridged methylene fluorene dimethylenediamine and 4, 4'-methylenebis(cyclohexylamine) and the like.

In particular, the thermoplastic polysiloxane constituting the present invention is considered in consideration of the aforementioned physical properties. The amine resin layer should suitably contain 50 to 100 mol% of the knot represented by the following [Chemical Formula 1] Construction unit.

The -X- contained in [Chemical Formula 1] is an aromatic diamine compound containing one or two or more selected from the following structures and which can be used singly or by copolymerization.

-X ₁ - is selected from the group consisting of -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -CONH-, -C(CF ₃ ) ₂ -, -(CH ₂ ) - or a combination thereof.

Included in [Chemical Formula 1] It is a dianhydride which contains one or two or more selected from the following structures and can be used singly or by copolymerization.

More specifically, a flexible metal clad laminate is provided wherein -X ₁ - is an aromatic diamine compound comprising -O- and is included A dianhydride selected from one or both of the following structures.

The thermoplastic polyimide-based resin layer according to the present invention should suitably contain 50 to 100 mol% of the structural unit represented by [Chemical Formula 1]. In the case where the content is less than 50 mol%, the storage modulus at 350 ° C is more than 1 X 10 ⁸ Pa, so that the flowability of the thermoplastic polyimide film at a high temperature is insufficient, so that thermal lamination cannot be performed. Process problems.

The polyimine-based resin mentioned in the present invention contains all resins having a quinone ring such as the following [Chemical Formula 2], and examples thereof may include polyimine, polyamidimide, polyester Yttrium imine, decane-modified polyimine, and the like. Further, in addition to the single substance of the polyimine-based resin, a mixture of the above-mentioned polyimine-based resin and another polymer resin is mixed. Further, it also contains a mixture of a polyimine-based resin and other additives such as a curing accelerator such as pyridine and quinoline, a coupling agent such as decane, an adhesion providing agent such as an epoxide, and coating. Defoamer and leveling agent that are easy to process.

The method for producing a flexible metal clad laminate of the present invention comprises a die casting method and a lamination method.

The flexible metal clad laminate produced by the die casting method is produced by applying a polyaminic acid resin (precursor of a polyimine resin) to the metal layer and via A thermal or chemical curing process is used to form a polyimine-based resin layer. Further, the double-sided flexible metal clad laminate is manufactured by thermally laminating a single-sided flexible metal clad laminate obtained by a die casting method with a metal layer. Also included in the die casting process.

A flexible metal clad laminate produced by lamination is produced by pre-manufacturing a resin layer having a thermoplastic polyimine system, a thermosetting polyimide tree The polyimine film layer of the multilayer structure of the resin layer of the resin layer and the thermoplastic polyimide layer is then laminated to one surface or both surfaces by thermal lamination to complete the manufacture.

Herein, the thermoplastic polyimide resin layer contains 50 to 100 mol% of a structural unit represented by [Chemical Formula 1], and, for example, pyromellitic dianhydride as a dianhydride and 1 as a diamine , 3-bis(4-aminophenoxy)benzene can be reacted such that the content of the structural unit is between 50 and 100 mol% based on the overall polyimine used to form the valine acid, and The imidization may be applied and heated to carry out the imidization reaction to produce a thermoplastic polyimide resin layer.

The thermosetting polyimine resin layer is not greatly limited, but according to an example of the present invention, p-phenylenediamine as a diamine and 4,4'-diaminodiphenyl ether and 3,3' as a dianhydride, 4,4'-diphenyltetracarboxylic dianhydride can be reacted so that the content is between 50 and 100 mol% based on the overall polyimine used to form the valine acid, and the guanamine can be applied. The acid is heated and heated to carry out the imidization reaction to produce a thermosetting polyimide resin layer.

In the next embodiment, the imidization is carried out by a dehydration condensation reaction, and the reaction temperature is preferably from 100 to 400 ° C and the reaction time required is from 10 minutes to 24 hours, but it is not required to be greatly limited.

As long as it can dissolve the polyamic acid as the precursor of the polyimine, the solvent used in the synthesis is not greatly limited, and an anthraquinone solvent such as dimethyl hydrazine and diethyl hydrazine or formamide can be used. Solvents such as N,N-dimethylformamide and N,N-diethylformamide, acetaminophen solvents such as N,N-dimethylacetamide and N,N-diethylacetamidine Amine, pyrrolidone solvent such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenolic solvent such as phenol, o-cresol, m-cresol or p-cresol, xylenol, halogenated phenol and children A tea phenol, an ether solvent such as diglyme, triglyme, tetraglyme, tetrahydrofuran and dihydroxy acid, an alcohol solvent such as methanol, ethanol and butanol, a cellosolve such as butyl A granule, hexamethylphosphoniumamine, γ-butyrolactone or the like, and these examples may preferably be used singly or in the form of a mixture, and an aromatic hydrocarbon such as xylene and toluene may be used.

The metal layer constituting the flexible metal clad laminate represents a conductive metal such as copper, aluminum, silver, palladium, nickel, chromium, molybdenum, and tungsten, and alloys thereof or mixtures thereof. In general, copper is widely used, but the metal layer is not limited thereto. Further, a metal layer of the present invention contains a substance in which the surface of the metal is subjected to physical or chemical surface treatment to increase the bonding strength between the metal clad layer and the resin layer.

Examples of the coating method that can be applied to the present invention include blade coating, roll coating, and mold Coating, curtain coating, etc., and the method is not limited as long as it satisfies the object pursued by the present invention. The previously semi-cured or fully cured polyimine solution and the polyimine precursor solution can be used as a coating solution.

The drying and curing treatment of the insulating layer can be selectively performed after coating, and various known methods such as hot air curing, IR curing, batch curing, continuous curing, and chemical curing can be carried out.

Hereinafter, the present invention will be described in detail by way of experimental examples. However, the invention is not limited to such examples.

The following abbreviations are used in the examples.

DMAc: N,N-dimethylacetamide

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

p-PDA: p-phenylenediamine

ODA: 4,4'-diaminodiphenyl ether

BAPP: 2,2-bis(4-aminophenoxy)phenylpropane

DABA: 3,5-diamino-benzoic acid

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

PMDA: pyromellitic dianhydride

BPADA: 4,4'-bisphenol A dianhydride

BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride

TMEG: ethylene glycol di(trimellitic dianhydride)

The physical properties mentioned in the present invention were measured according to the following methods.

●Linear thermal expansion coefficient

The linear thermal expansion coefficient was measured under the following conditions: a temperature rise from 30 ° C to 400 ° C at a heating rate of 5 ° C / min under a nitrogen atmosphere, during which a tension of 0.03 N was applied using TMA/SDTA 861e manufactured by Mettler-Toledo GmbH. The average value of the linear thermal expansion coefficient is measured between 25 ° C and 200 ° C at 25 ° C as an interval, and the measured value is regarded as a linear thermal expansion coefficient between 100 ° C and 200 ° C.

●Storage modulus

The storage modulus was measured under the following conditions: from 30 ° C to 400 ° C at a heating rate of 5 ° C / min under a nitrogen atmosphere, during which Mettler-Toledo GmbH was used. The DMA/SDTA 861e applies a tension of 0.1 N, a frequency of 10 Hz, and a displacement of 30 um.

● glass transition temperature

The DMA was used under the same conditions as the measured storage modulus, and the maximum value of Tan δ obtained at this time was regarded as the glass transition temperature.

●Evaluation of thermoplastic polyimine

In the thermoplastic polyimide-based resin mentioned in the present invention, a polyimide-based resin having a storage modulus of 1×10 ⁸ Pa or less at 350 ° C is considered to be a thermoplastic polyimide-based resin. The resin, and a polyimine-based resin having a storage modulus of 1 X 10 ⁸ Pa or higher at 350 ° C is considered to be a thermosetting polyimide-based resin. The measurement of the stored modulus is based on the above method.

● Impedance to solder after absorbing moisture

The sample having a size of 5 cm X 5 cm was pretreated at a setting of 40 ° C and 90% relative humidity for 72 hours or more, and then the sample was immersed in a solder bath at 300 ° C. The case where no appearance defects such as swelling and layer separation were caused was confirmed as passing, and the case where the appearance was defective was judged as not passing. In a single-sided copper clad laminate type, samples with copper foil and insulating layers were evaluated without the need to remove copper foil. In the type of the double-sided copper clad laminate, the copper foil on one side was removed and evaluated and each side was evaluated separately.

●Adhesion strength with copper foil

The measurement was performed based on JIS-C6471.

[Synthesis Example 1]

After the p-PDA and ODA at a molar ratio of 90:10 at room temperature were completely dissolved in DMAc, 100.9 mol% of BPDA was gradually added to the solution. The mixture was allowed to react at room temperature for 24 hours. In this case, the solid content of the entire solution was set to 13% by weight.

[Synthesis Examples 2 to 5]

The production was carried out according to the components and contents shown in [Table 1] using the same production conditions as in Synthesis Example 1.

[Example 1]

The polyamine acid solution produced by [Synthesis Example 2] was applied to an electrolytic copper foil (F2WS copper foil manufactured by Furukawa circuit foil, roughness Rz = 2.0 μm) having a thickness of 12 μm, followed by drying at 140 ° C. A first polyimine precursor layer is formed. The polyamic acid solution produced through [Synthesis Example 1] was applied to one surface of the first polyimideimine precursor layer, followed by drying at 140 °C to form a second polyimideimide precursor layer. Thereafter, a polyamic acid solution produced through [Synthesis Example 2] was applied to one surface of the second polyimideimide precursor layer, followed by drying at 140 ° C to form a third polyimideimide precursor layer. . The resulting laminate was heated from 150 ° C to 385 ° C for 9 minutes under a nitrogen atmosphere. After curing, each of the first polyimideimine precursor layer, the second polyimideimine precursor layer, and the third polyimideimine precursor layer has a thickness of 2.5 um, 14 um, and 3 um, respectively. The characteristics of the laminate were evaluated and the results are shown in [Table 2].

[Example 2]

By the same method as in Example 1, the flexible layer was fabricated according to the film layer composition of [Table 2]. Metal clad laminate.

[Comparative Examples 1 to 3]

A flexible metal clad laminate was produced according to the film layer constitution of [Table 2] by the same method as in Example 1.

Claims (7)

A flexible metal clad laminate in which a metal layer is formed on one surface or both surfaces of an insulating layer composed of a plurality of polyimine-based resin layers, and the plurality of polyimine-based resin layers a plurality of thermoplastic polyimide-based resin layers, a thermosetting polyimide-based resin layer, and a thermoplastic polyimide-based resin layer sequentially laminated to the metal layer The yttrium-based resin layer has a storage elastic modulus of 1×10 ⁸ Pa or higher at 300 ° C and a storage elastic modulus of 1×10 ⁸ Pa or less at 350 ° C. The flexible metal clad laminate of claim 1, wherein the polyimine resin layer in contact with the metal layer has a density of 1×10 ⁸ to 1×10 ¹⁰ Pa at 300 ° C. The modulus was stored and had a storage modulus of 1 X 10 ⁵ to 1 X 10 ⁸ Pa at 350 °C. The flexible metal clad laminate according to claim 1, wherein the polyimine-based resin layer in contact with the metal layer is a thermoplastic polyimide system having a glass transition temperature of 300 ° C or lower. The resin layer. The flexible metal clad laminate according to claim 1, wherein the polyimide layer in contact with the metal layer has a linearity measured at a temperature ranging from 100 ° C to 200 ° C. The coefficient of thermal expansion is 50 ppm/K or less. The flexible metal clad laminate according to any one of claims 1 to 4, wherein the resistance to solder after absorption of moisture after treatment for 72 hours at 40 ° C and 90% relative humidity The temperature is 300 ° C or higher and the adhesion strength to the metal layer is 1.0 kgf / cm or more. The flexible metal clad laminate according to any one of claims 1 to 4, wherein the polyimine-based resin layer in contact with the metal layer contains 50 to 100 mol% of the following Structural unit represented by [Chemical Formula 1]: [Chemical Formula 1] -X- contained in [Chemical Formula 1] is an aromatic diamine compound containing one or two or more selected from the following structures and which can be used singly or by copolymerization, -X ₁ - is selected from the group consisting of -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -CONH-, -C(CF ₃ ) ₂ -, -(CH ₂ )- or a combination thereof, and contained in [Chemical Formula 1] It is a dianhydride comprising one or two or more selected from the following structures and can be used alone or by copolymerization: The flexible metal clad laminate according to claim 6, wherein -X ₁ - is an aromatic diamine compound containing -O-, and A dianhydride comprising one or two or more of the following structures: