KR101763873B1 - Flexible metal laminate - Google Patents

Abstract

The present invention relates to a polyimide resin composition comprising 30 to 95% by weight of a polyimide resin having a specific chemical structure in which at least one aliphatic, alicyclic, or aromatic functional group of a long chain, substituted or unsubstituted with halogen, is substituted at one or more terminals; And a polyimide resin layer containing 5 to 70% by weight of fluoric resin particles.

Description

[0001] FLEXIBLE METAL LAMINATE [0002]

The present invention relates to a flexible metal laminate, and more particularly, to a flexible metal laminate capable of securing a low permittivity and a low dielectric loss factor while having a high elasticity and a low moisture absorption rate.

In recent years, signal transmission speed within the electronic device or signal transmission speed to the outside of the electronic device has been accelerating in accordance with the trend of miniaturization and high speed of electronic devices and the combination of various functions. Accordingly, a printed circuit board using an insulator having a dielectric constant and a dielectric loss coefficient lower than that of an existing insulator is required.

As reflected in this tendency, there is a tendency to apply LCP (Liquid Crystalline Polymer), which is an insulator less susceptible to moisture absorption, than a conventional polyimide even in a flexible printed circuit board. However, even when the LCP is applied, the degree of improvement due to application is insignificant because the dielectric constant (Dk = 2.9) of LCP is substantially not different from that of polyimide (Dk = 3.2) substantially and the heat resistance of the LCP becomes a problem in the soldering process And since the LCP has thermoplasticity, there is a problem that compatibility with the PCB manufacturing process using the conventional polyimide is inferior in the laser hole processing using the laser.

Accordingly, efforts have been made to lower the dielectric constant of polyimide used as an insulator of conventional flexible circuit boards. For example, U.S. Patent No. 4,816,516 discloses a method of molding a molded article by mixing polyimide and a fluorine-based polymer. However, the above patent does not relate to a product for an electronic device requiring a low dielectric constant but relates to a molded product, and polyimide having a large coefficient of thermal expansion and a low glass transition temperature is used. In addition, in order to be used for a printed circuit board, a polyimide resin must be processed in the form of a thin film. The US patent does not disclose a thin-film-type copper-clad laminate.

Further, U.S. Patent No. 7026032 discloses a method of lowering the dielectric constant of a product produced by dispersing a fine powder of a fluorine-based polymer in polyimide. The US patent discloses that the fluorine-based polymer fine powder is more distributed on the outer surface than the inner core of the insulator. However, since the content of the fluorinated polymer is large in the outermost layer of the insulator as described in the above-mentioned U.S. patent, moisture permeation and absorption are lowered by the fluorinated polymer on the outer surface, and the overall water absorption rate can be lowered. However, There is a problem that the copper clad laminate does not exist.

For example, the polyimide resin described in the U.S. patent may weaken the adhesive force with the coverlay or the adhesion with the prepreg, and the adhesive force with the ACF may be lowered, and the coefficient of thermal expansion (CTE) of the polyimide resin disclosed in the above- Since the fluoropolymer is present in excess on the surface of the polyimide resin, the fluoropolymer can be melted at a temperature of about 380 ° C, which is applied to the holding process during the PCB manufacturing process There is a risk that the copper foil circuit will peel off from the insulator.

Previously, in order to lower the dielectric constant of the insulator, a method of adding an additional component or a method of raising the temperature of the metal laminate or the sintering temperature of the PCB was used. However, according to this method, The elastic modulus of the final product to be produced may be lowered or the thermal expansion coefficient may be greatly increased.

(Prior Art Document 001) U.S. Patent No. 4,816,516 (Prior Art Document 002) United States Patent No. 7026032

The present invention is intended to provide a flexible metal laminate capable of securing a low permittivity and a low dielectric loss coefficient while having a high elasticity and a low moisture absorption rate.

In the present specification, an aliphatic functional group having at least 6 carbon atoms which is substituted or unsubstituted with a halogen, an alicyclic functional group having at least 6 carbon atoms, which is substituted or unsubstituted with at least one halogen, and an aromatic functional group having at least 6 carbon atoms, 30 to 95% by weight of a polyimide resin having at least one functional group selected from the group consisting of the repeating units of the following formula (1) substituted at one or more ends thereof; And a polyimide resin layer containing 5 to 70% by weight of fluoric resin particles.

 [Chemical Formula 1]

Wherein Y ₁ is a tetravalent aromatic organic functional group, X is a divalent aromatic organic functional group, and n is an integer of 1 to 300.

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

As described above, according to one embodiment of the present invention, an aliphatic functional group having at least 6 carbon atoms, at least one of which is substituted or unsubstituted with a halogen, an alicyclic functional group having at least 6 carbon atoms, which is substituted or unsubstituted with at least one halogen, From 30 to 95% by weight of a polyimide resin containing at least one functional group selected from the group consisting of unsubstituted aromatic groups having 6 or more carbon atoms and having a repeating unit of the formula (1); And a polyimide resin layer containing 5 to 70% by weight of fluoric resin particles.

The inventors of the present invention have found that a flexible metal laminate comprising a polyimide resin and a polyimide resin layer containing a fluorine resin having repeating units of the following formula (1) wherein the above-mentioned specific functional group is substituted at the terminal has high elasticity and low water absorption And it is possible to secure a lower dielectric constant and a low dielectric loss coefficient while having the above-mentioned characteristics.

Specifically, an aliphatic functional group having at least 6 carbon atoms, at least one of which is substituted or unsubstituted with a halogen, an alicyclic functional group having at least 6 carbon atoms, which is substituted or unsubstituted with at least one halogen, and an aromatic functional group having at least 6 carbon atoms, The polyimide resin in which at least one functional group selected from the group is substituted at one or more ends thereof allows the fluoric resin particles to be evenly distributed over the entire area of the polyimide resin layer, And the dielectric loss coefficient of the polyimide resin layer included therein can be greatly lowered.

As the functional groups described above are substituted at the ends of the polyimide resin, the fluorine resin particles can be dispersed in the polyimide resin layer in a uniform size, and accordingly, the polyimide resin layer and the flexible metal laminate The sieve may have a lower dielectric loss factor.

 Specifically, the volume of the fluororesin particles having a particle diameter of 0.1 占 퐉 to 20 占 퐉 in the polyimide resin may be 80% or more, or 80% to 90% of the total volume of the fluororesin particles.

The fluororesin may include particles having a longest diameter of 0.05 mu m to 30 mu m, or 0.1 mu m to 20 mu m. If the maximum diameter of the fluorine-based resin is too small, the surface area of the fluorine-based resin may be increased to deteriorate the physical properties of the polymer resin layer or increase the amount of the dispersing agent to be described later. If the maximum diameter of the fluororesin is too large, the surface properties of the polymer resin layer to be produced may be deteriorated or the dispersibility of the polymer composition solution for producing the polymer resin layer may be deteriorated.

The longest diameter of the fluororesin particles means the longest diameter of a single particle. When such fluororesin particles aggregate, particles having a longest diameter of several tens to several hundreds of micrometers may be formed.

As described above, since the fluororesin particles can be dispersed in a uniform size in the polyimide resin layer, the polyimide resin contains 0.1 part or less of the aggregated whole of the single particles of the fluororesin and the single particles of the fluororesin A single particle or agglomerate having a particle size in the range of 탆 to 20 탆 may be in a range of 80% or more, or 80% to 90% of the total volume.

In addition, the polyimide resin layer may have a dielectric loss factor (Df) of 0.0015 or less, or 0.0010 to 0.0015, or 0.0010 to 0.0014 at 10 GHz in a dry state.

Further, the polyimide resin layer may have a dielectric loss factor (Df) of not more than 0.0099 at 10 GHz, or 0.0090 to 0.0099, or 0.0095 to 0.0098 at wet state.

On the other hand, as described above, at the terminal of the polyimide resin, at least one aliphatic functional group having at least 6 carbon atoms substituted or unsubstituted with halogen, at least one alicyclic functional group having at least 6 carbon atoms substituted or unsubstituted with halogen, Or an unsubstituted aromatic group having 6 or more carbon atoms may be substituted at one or more ends of the functional group.

Specific examples of the functional group substituted at the terminal of the polyimide resin include linear or branched aliphatic or alicyclic functional groups having 4 to 30 carbon atoms which are substituted or unsubstituted by halogen; An alkylaryl group having 7 to 40 carbon atoms which is substituted or unsubstituted with at least one halogen; Or an arylalkyl group having 7 to 40 carbon atoms which is substituted or unsubstituted with at least one halogen.

More specific examples of the functional group substituted at the terminal of the polyimide resin include a linear alkyl group having 8 to 20 carbon atoms, a perfluoro alkyl group having 8 to 20 carbon atoms, a linear alkyl group having 8 to 20 carbon atoms A substituted phenyl group; Or a phenyl group substituted with a straight chain perfluoro alkyl group having 8 to 20 carbon atoms.

In the present specification, an aryl group means a functional group derived from arene, an alkylaryl group means an aryl group substituted with an alkyl group, and an arylalkyl group means an alkyl group substituted with an aryl group.

Y ₁ in the formula (1) may be a tetravalent group selected from the group consisting of the following formulas (21) to (27).

[Chemical Formula 21]

[Chemical Formula 22]

In Formula 22, Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) n2 O-, or -OCO (CH _{2) n3} a OCO-, wherein n1, n2 and n3 is an integer of 1 to 10, respectively.

 (23)

Y ₂ and Y ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 - _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, wherein n1, n2, and and n3 is an integer of 1 to 10, respectively.

≪ EMI ID =

In the above formula (24), Y ₄ , Y ₅ And Y ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} a OCO-, wherein n1, n2 and n3 is 1 to 10 - -CONH-, -COO-, - (CH 2) n1 It is an integer.

(25)

(26)

(27)

In the above Formulas 21 to 27, '*' means a bonding point.

In order to ensure the optimized thermal expansion coefficient of the soft metal laminate according to one embodiment of the present invention with a high elasticity while having a lower dielectric constant and a low moisture absorption rate, Y ₁ in the formula ₁ is selected from the group consisting of the following formulas 4 is a functional group. The Y ₁ may be the same or different in each of the repeating units of the formula (1).

(28)

[Chemical Formula 29]

(30)

In the above Chemical Formulas 28 to 30, '*' means a bonding point.

In the above formula (1), X may be a divalent functional group selected from the group consisting of the following formulas (31) to (34).

(31)

Wherein R ₁ is selected from the group consisting of hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(32)

Wherein L ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) and _{n2 O-, -OCH 2 -C (CH} 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 is an integer from 1 to 10, R ₁ and R ₂ may be the same or different from one another, each _{hydrogen, -CH 3, -CH 2 CH 3} , -CH 2 CH 2 CH 2 CH 3, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(33)

L ₂ and L ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or - a OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 is an integer from 1 to 10, R _1, R ₂ and R ₃ may be the same or different from one another, each hydrogen, -CH _3, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(34)

In the above formula (34), L ₄ , L ₅ And L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{-CONH-, -COO-, - (CH 2} ) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO -, and wherein n1, n2 and n3 is an integer from 1 to 10, R _1, R _2, R ₃ and R ₄ may be the same or different from one another, each _{hydrogen, -CH 3, -CH 2 CH 3} , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

In particular, when X in the above formula (1) is a divalent functional group represented by the following chemical formula (35), the flexible metal laminate of this embodiment can have a lower dielectric constant and a lower water absorption rate and can secure an optimized thermal expansion coefficient . X may be the same or different in each of the repeating units of the formula (1).

 (35)

In the above formula (35), R ₁ and R ₂ may be the same or different from each other and each represents -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

In the above formula (1), X may be a divalent functional group selected from the group consisting of the following formulas (31) to (34).

(31)

Wherein R ₁ is selected from the group consisting of hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(32)

Wherein L ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) and _{n2 O-, -OCH 2 -C (CH} 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 is an integer from 1 to 10, R ₁ and R ₂ may be the same or different from one another, each _{hydrogen, -CH 3, -CH 2 CH 3} , -CH 2 CH 2 CH 2 CH 3, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(33)

L ₂ and L ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or - a OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 is an integer from 1 to 10, R _1, R ₂ and R ₃ may be the same or different from one another, each hydrogen, -CH _3, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

(34)

In the above formula (34), L ₄ , L ₅ And L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{-CONH-, -COO-, - (CH 2} ) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO -, and wherein n1, n2 and n3 is an integer from 1 to 10, R _1, R _2, R ₃ and R ₄ may be the same or different from one another, each _{hydrogen, -CH 3, -CH 2 CH 3} , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

In particular, when X in the above formula (1) is a divalent functional group represented by the following chemical formula (35), the flexible metal laminate of this embodiment can have a lower dielectric constant and a lower water absorption rate and can secure an optimized thermal expansion coefficient . X may be the same or different in each of the repeating units of the formula (1).

 (35)

In the above formula (35), R ₁ and R ₂ may be the same or different from each other and each represents -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₂ CF ₃ Lt; / RTI >

The polyimide resin may include 75 mol% or more, or 75 mol% to 100 mol% of the repeating unit represented by the formula (1). The polyimide resin may contain other polyimide repeating units other than the repeating unit of the above-mentioned formula (1), for example, the Y ₁ is an aliphatic or alicyclic tetravalent organic functional group, or X is an aliphatic or alicyclic tetravalent organic functional group , And the content of other such other polyimide repeating units may be 25 mol% or more, or 0 to 25 mol%.

The polyimide resin may have a weight average molecular weight of 3,000 to 600,000, or 50,000 to 300,000. If the weight average molecular weight of the polyimide resin is too small, it is impossible to sufficiently secure the mechanical properties required in the application of the flexible metal laminate or the like. Also, if the weight average molecular weight of the polyimide resin is too large, the elasticity of the polymer resin layer may be lowered.

The polyimide resin layer may have a thickness of 0.1 탆 to 100 탆, or 1 탆 to 50 탆.

The fluororesin particles may be selected from the group consisting of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene Based polymer comprising at least one member selected from the group consisting of copolymer resin (ETFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE) and ethylene-chlorotrifluoroethylene resin (ECTFE) .

The polyimide resin layer may contain 5 to 70% by weight of the fluororesin particles. If the content of the fluoric resin particles in the polyimide resin layer is too small, the resulting flexible metal laminate may not have a sufficiently low dielectric constant or water absorption rate. If the content of the fluoric resin particles in the polyimide resin layer is too large, the mechanical properties of the flexible metal laminate may be deteriorated and easily torn or broken. In addition, The thermal expansion coefficient of the mid resin layer can be greatly increased.

The flexible metal laminate of one embodiment may include the polyimide resin layer and the metal thin film, and the metal thin film may be formed of copper, iron, nickel, titanium, aluminum, silver, gold, ≪ / RTI >

The metal thin film may be laminated on at least one surface of the polyimide resin layer. Specifically, the flexible metal laminate may include one metal thin film, and the soft metal laminate may include two metal thin films opposed to each other. In this case, And can be located between two opposing metal thin films.

The ten point average roughness Rz of the surface of the metal thin film may be 0.5 탆 to 2.5 탆. If the ten-point average roughness of the surface of the metal thin film is too small, the adhesion to the polyimide resin layer may be lowered. If the average roughness of the ten points of the metal thin film surface is too large, surface roughness may increase and the transmission loss may increase in the high- .

The metal thin film may have a thickness of 0.1 탆 to 50 탆.

The above-described flexible metal laminate may further comprise a thermoplastic polyimide resin layer formed on at least one side of the polyimide resin layer. The thermoplastic polyimide resin layer may have the same or different composition as the polyimide resin contained in the polyimide resin layer.

The thermoplastic polyimide resin layer may have a thickness the same as or different from that of the polyimide resin layer, and may have a thickness in the range of 0.1 탆 to 100 탆, or 1 탆 to 50 탆.

On the other hand, the method for producing the above-described flexible metal laminate is not particularly limited, and a commonly known method for synthesizing a polyimide resin and a method for producing a flexible metal laminate can be used.

The polyimide resin contained in the polyimide resin layer can be obtained by applying and drying a polymer resin solution containing polyamic acid as a precursor, followed by heat treatment at a high temperature of 250 ° C to 400 ° C.

The polyamic acid, which is a precursor of the polyimide resin, can be obtained by reacting a tetracarboxylic acid or an anhydride thereof with a diamine compound. For example, the tetracarboxylic acid having a tetravalent group selected from the group consisting of Formulas 21 to 27 A tetracarboxylic acid or an anhydride thereof with a diamine compound containing a divalent functional group selected from the group consisting of the above formulas (31) to (34), wherein the aliphatic functional group having at least 6 carbon atoms, which is substituted or unsubstituted with halogen, halogen An aromatic compound having at least one functional group selected from the group consisting of a substituted or unsubstituted alicyclic group having at least 6 carbon atoms and at least one substituted or unsubstituted aromatic group having at least 6 carbon atoms substituted with at least one halogen, Wherein said specific functional group is a substituted poly Oh, the acid can be synthesized.

The resin composition including the polyamic acid and the fluororesin, which are precursors of the polyimide, may include an organic solvent. Examples of usable organic solvents include, but are not limited to, N, N'-dimethylformamide, N, N, N'-diethylacetamide, N, N'-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimetol sulfone, m- , Anisole, etc., may be used alone or in combination of two or more. At this time, the usable amount of the organic solvent may be about 2 to 8 times the total solid content of the resin composition.

According to the present invention, it is possible to provide a flexible metal laminate capable of securing a low permittivity and a low dielectric loss coefficient while having a high elasticity and a low moisture absorption rate.

The flexible metal laminate can greatly reduce the dielectric constant and dielectric loss coefficient of the substrate material and can greatly reduce the signal transmission loss proportional to the dielectric constant and the dielectric loss coefficient so that it is possible to provide a circuit system having a very low transmission loss even in a highly integrated micro module .

Further, by using the flexible metal laminate, it is possible to make the printed circuit board thinner while matching the impedances, so that the thickness of various electronic products and electronic devices themselves can be greatly reduced and the line width of the printed circuit board can be widened, The defective rate of the product is largely lowered and the manufacturing cost can be reduced.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Manufacturing example : Polyamic acid  Preparation of solution]

Production Example 1 : Containing fluorine resin Polyamic acid  Preparation of solution ( P1 )

1 L of a polyethylene bottle was charged with nitrogen, and 765 g of a 1: 1 mixed solvent of n-methyl-2-pyrrolidone, a polytetrafluoroethylene micropowder (particle size: about 0.2 to 3.0 Mu m) and 765 g of a bead having a diameter of 2 mm were placed and stirred in a high-speed ball milling machine.

16 g of a solution in which the PTFE microparticle was dispersed, 107 g of dimethylacetamide, 13 g of pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4 ' -Diaminobiphenyl were charged and reacted with stirring with a stirrer while flowing nitrogen at 50 占 폚 for 10 hours.

0.39 g of 1-octadecaneamine was added to the reaction product, and the mixture was allowed to react at 50 캜 for 5 hours while stirring with a stirrer while stirring for 5 hours to obtain a polyamic acid solution (P1) having a viscosity of 26,000 cP.

Manufacturing example  2 to 7: containing fluorine resin Polyamic acid  Preparation of solution

A polyamic acid solution was obtained in the same manner as in Preparation Example 1, except that the compound of the following Table 1 was used in place of 0.39 g of 1-octadecaneamine, and 10 g of the PTFE micropowder-dispersed solution was used.

division compound Production Example 2 0.39 g of 1-octadecane amine Production Example 3 0.39 g of 4- (heptadecafluorooctyl) aniline Production Example 4 0.39 g of 4-decyl aniline Production Example 5 0.39 g of 4-tetradecyl aniline Production Example 6 0.39 g of 4-hexaethylaniline Production Example 7 0.39 g of 4-octadecyl aniline

Production Example 8 : Containing fluorine resin Polyamic acid  Preparation of solution

1 L of a polyethylene bottle was filled with nitrogen, 765 g of a 1: 1 mixed solvent of dimethylacetamide and 1-methyl-2-pyrrolidone, a polytetrafluoroethylene micropowder (PTFE micro powder, particle size: About 1.0 to 5.0 mu m) and 765 g of a bead having a diameter of 2 mm were placed and stirred in a high-speed ball milling machine.

16 g of a solution in which the PTFE micropowder was dispersed, 107 g of dimethylacetamide, 13 g of pyromellitic dianhydride and 20 g of 4-decylaniline were placed in a 500-mL round bottom flask and nitrogen was flowed at 50 ° C for 10 hours The reaction was carried out with stirring using a stirrer to obtain a polyamic acid solution (P3) having a viscosity of about 25,000 cps.

[ Example  And Comparative Example : Soft metal Of the laminate  Produce]

Example 1

The polyamic acid solution prepared in Preparation Example 1 was coated on a matte surface of a copper foil (thickness: 12 μm) so as to have a final thickness of 2 μm, followed by drying at 120 ° C. for 10 minutes. The polyamic acid solution (P2) obtained in Preparation Example 2 was coated on the dried polyamic acid solution layer to a thickness of 20 탆 and dried at 120 캜 for 10 minutes. Then, the polyamic acid solution (P3) obtained in Preparation Example 3 was coated on the dried polyamic acid solution (P2) layer to a thickness of 2 占 퐉 and dried at 120 占 폚 for 10 minutes to prepare a laminate.

The final dried laminate was placed in an oven and thermoset for 30 minutes at a temperature of about 300 ° C and a nitrogen atmosphere.

After the thermosetting, the outermost layer (the layer in which the polyamic acid solution (P3) was applied and dried) of the laminate was brought into contact with the matte surface of the copper foil (thickness: 12 mu m) and pressed at 400 DEG C, A flexible metal laminate was produced.

Example  2 to 7

A flexible metal laminate was prepared in the same manner as in Example 1, except that the polyamic acid solution prepared in each of Production Examples 2 to 7 was used.

Comparative Example  One

A flexible metal laminate having copper foils on both sides was prepared in the same manner as in Example 1, except that the polyamic acid solution obtained in Preparation Example 8 was used in place of the polyamic acid solution prepared in Preparation Example 1. [

[ Experimental Example ]

One. Experimental Example 1 : Soft metal Of the laminate  Property measurement

The dielectric constant and dielectric loss coefficient of the copper clad laminate obtained in the above Examples and Comparative Examples were measured as follows and the results are shown in Table 2 below.

(1) Measurement of dry dielectric constant and dielectric loss factor

The flexible metal laminate obtained in Examples and Comparative Example was etched to remove the copper foil by etching, and the polyimide resin laminate was dried at 150 占 폚 for 30 minutes. The dielectric constant of the polyimide resin laminate was measured by a split post dielectric resonance (SPDR) method , The dielectric constant and dielectric loss factor were measured using an Agiletn E5071B ENA apparatus at 25 ° C and 50% RH.

(2) Measurement of wet dielectric constant and dielectric loss coefficient

The flexible metal laminate obtained in Examples and Comparative Examples was etched to remove the copper foil by etching, and the polyimide resin laminate was immersed in distilled water for about 24 hours. Then, the polyimide resin laminate was taken out from the distilled water to remove the water on the surface, and the dielectric constant and the dielectric loss were measured using an Agiletn E5071B ENA apparatus under the conditions of 25 ° C and 50% RH by SPDR (split post dielectric resonance) The coefficients were measured.

The measurement result of Experimental Example 1 division Measurement results of Experimental Example 2 Dielectric loss factor
(Df) @ 5 GHz
[Dry state] Dielectric loss factor
(Df) @ 5 GHz
[Wet state] Example 1 0.0013 0.0097 Comparative Example 0.0016 0.0100

As shown in Table 2, it was confirmed that the polyimide resin layer included in the flexible metal clad laminate of Examples had a lower dielectric loss coefficient in the dry and wet state than the soft metal clad laminate of the comparative example in the dry state and the wet state.

As a result of introducing at least one long-chain aliphatic, alicyclic or aromatic functional group having at least 6 carbon atoms substituted or unsubstituted with halogen at the terminal of the polyimide resin in the polyimide resin layer contained in the flexible metal clad laminate of the embodiment, It can be evenly distributed over the entire area with a more uniform size, and accordingly, the dielectric loss coefficient of the polyimide resin layer included in the flexible metal clad laminate is also lowered.

Claims (15)

An aliphatic functional group having at least 6 carbon atoms which is substituted or unsubstituted with halogen, an alicyclic functional group having at least 6 carbon atoms substituted or not substituted with at least one halogen, and an aromatic functional group having at least 6 carbon atoms substituted or unsubstituted with halogen From 30 to 95% by weight of a polyimide resin having at least one functional group substituted at one or more ends thereof and containing a repeating unit represented by the following formula (1); And
And a polyimide resin layer containing 5 to 70% by weight of fluoric resin particles,
Wherein the polyimide resin layer has a dry state and a dielectric loss factor (Df) of less than or equal to 0.0015 at 10 GHz.
[Chemical Formula 1]

Wherein Y ₁ is a tetravalent aromatic organic functional group, X is a divalent aromatic organic functional group,
And n is an integer of 1 to 300.
The method according to claim 1,
Wherein the volume of the fluororesin particles having a particle diameter of 1 占 퐉 to 20 占 퐉 is 80% or more of the total volume of the fluororesin particles.
delete The method according to claim 1,
Wherein the polyimide resin layer has a dielectric loss factor (Df) of less than 0.0099 at 10 GHz in a wet state.
The method according to claim 1,
The functional group substituted at the terminal of the polyimide resin may be a linear or branched aliphatic or alicyclic functional group having 4 to 30 carbon atoms which is substituted or unsubstituted with at least one halogen; An alkylaryl group having 7 to 40 carbon atoms which is substituted or unsubstituted with at least one halogen; And an arylalkyl group having 7 to 40 carbon atoms which is substituted or unsubstituted with at least one halogen,
Flexible metal laminate.
The method according to claim 1,
The functional group substituted at the terminal of the polyimide resin is,
A straight chain alkyl group having 8 to 20 carbon atoms, a perfluoro alkyl group having 8 to 20 carbon atoms, a phenyl group substituted with a straight chain alkyl group having 8 to 20 carbon atoms; Or a phenyl group substituted with a straight chain perfluoro alkyl group having 8 to 20 carbon atoms.
The method according to claim 1,
Wherein Y < ₁ > is a tetravalent group selected from the group consisting of the following chemical formulas (21) to (27)
[Chemical Formula 21]

[Chemical Formula 22]

In Formula 22, Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to _{10, - -COO-, - (CH 2} ) n1
(23)

Y ₂ and Y ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, - (CH 2) O-, and _n2, or -OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 Are each an integer of 1 to 10,
≪ EMI ID =

In the above formula (24), Y ₄ , Y ₅ And Y ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} a OCO-, wherein n1, n2 and n3 is 1 to 10 - -CONH-, -COO-, - (CH 2) n1 Lt; / RTI &
(25)

(26)

(27)

In the above Formulas 21 to 27, '*' means a bonding point.
The method according to claim 1,
Wherein X is a divalent functional group selected from the group consisting of the following chemical formulas (31) to (34):
(31)

Wherein R ₁ is selected from the group consisting of hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF ₃ ego,
(32)

Wherein L ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) and _{n2 O-, -OCH 2 -C (CH} 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO-, wherein n1, n2 and n3 are each an integer of 1 to 10,
R ₁ and R _{2, which} may be the same or different, are each hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ ego,
(33)

L ₂ and L ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or - a OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to 10,
R _{1 ,} R ₂ and R ₃ may be the same or different and are each hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , - CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ ego,
(34)

In the above formula (34), L ₄ , L ₅ And L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{-CONH-, -COO-, - (CH 2} ) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO -, n1, n2 and n3 are each an integer of 1 to 10,
R _{1 ,} R ₂ , R ₃ and R ₄ may be the same or different and are each hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ ego,
In the above Formulas 31 to 34, '*' means a bonding point.
The method according to claim 1,
Wherein the polyimide resin comprises at least 75 mol% of the repeating unit represented by the formula (1).
The method according to claim 1,
Wherein the polyimide resin contained in the polyimide resin layer has a weight average molecular weight of 3,000 to 600,000.
The method according to claim 1,
Wherein the polyimide resin layer has a thickness of 0.1 mu m to 100 mu m,
The method according to claim 1,
The fluororesin particles may be selected from the group consisting of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene And at least one compound selected from the group consisting of copolymer resin (ETFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE) and ethylene-chlorotrifluoroethylene resin (ECTFE) Metal laminate.
The method according to claim 1,
And at least one metal thin film including at least one selected from the group consisting of copper, iron, nickel, titanium, aluminum, silver, gold, and two or more alloys thereof.
14. The method of claim 13,
Wherein the metal thin film has a thickness of 0.1 占 퐉 to 50 占 퐉.
The method according to claim 1,
And a thermoplastic polyimide resin layer formed on at least one side of the polyimide resin layer.