WO2014010968A1

WO2014010968A1 - Flexible metal laminate sheet

Info

Publication number: WO2014010968A1
Application number: PCT/KR2013/006214
Authority: WO
Inventors: 박영석; 박순용; 장세명
Original assignee: 주식회사 엘지화학
Priority date: 2012-07-11
Filing date: 2013-07-11
Publication date: 2014-01-16

Abstract

The present invention relates to a flexible metal laminate sheet comprising a polymer resin layer including a polyimide resin having a specific structure and a fluorine-based resin. More fluorine-based resin is distributed on the inside of the polymer resin layer than at the surface of the polymer resin layer.

Description

【Specification】

[Name of invention]

Ductile metal laminate

[Technical Field]

The present invention relates to a flexible metal laminate, and more particularly, to a flexible metal laminate having a low dielectric constant and a low water absorption rate and having a high elasticity and an optimized coefficient of thermal expansion.

[Technology behind the invention]

In recent years, in accordance with the trend of miniaturization, high speed, and various functions of electronic devices, a signal transmission speed inside an electronic device or a signal transmission speed outside the electronic device is increasing. Accordingly, there is a need for a printed circuit board using an insulator having a lower dielectric constant and lower dielectric loss coefficient than the conventional insulator.

Reflecting this trend, there is a movement to apply Liquid Crystalline Polymer (IXP), which is an insulator that is lower in dielectric constant and less affected by hoping, in a flexible printed circuit board. However, even if LCP is applied, the dielectric constant (Dk = 2.9) of LCP is not substantially different from that of polyimide (Dk = 3.2). Therefore, the improvement of application is insignificant, and the heat resistance of IXP is a problem in the soldering process. Low and because IXP has a thermoplastic, there is a problem that the compatibility with the PCB manufacturing process using a conventional polyimide in the via hole processing using a laser is inferior.

Therefore, as a solution to this, efforts have been made to lower the dielectric constant of polyimide, which is used as an insulator of a conventional flexible circuit board. For example, according to US Patent No. 4816516, a content of making a molded article by mixing polyimide and fluorine-based polymer is shown. However, the patent does not relate to products for electronic devices requiring a low dielectric constant but to molded articles, and uses polyimide having a high thermal expansion coefficient and a low glass transition rate. In addition, in order to use in a printed circuit board, polyimide resin should be processed in the form of a thin film. The content regarding the copper foil laminated board manufactured in the form is not shown. In addition, US 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 a polyimide. The U.S. Patent discloses that the bloso-based polymer fine powder is more distributed on the outer surface than the inner core of the insulator. However, as described in the U.S. patent, since the content of the fluorine-based polymer in the outermost layer of the insulator has a high water permeation and absorption is lowered by the fluorine-based polymer on the outer surface, but the overall water absorption rate can be lowered, the ductility of the existing polyimide Problems that copper foil laminates do not have may occur. For example, the polyimide resin described in the US patent may have a weak adhesion to the coverlay or prepreg and a low ACF, and the coefficient of thermal expansion (CTE) of the polyimide resin described in the US patent may be soft. In addition to being too large to be applied to copper foil laminates, the surface of the polyimide resin has an excessive amount of fluorine resin on the outside, so that the fluorine resin may be melted at a temperature of about 380 ° C that is applied to the storage process during the PCB manufacturing process. There is a risk of the copper foil circuit peeling off the insulator. Accordingly, in order to make low dielectric constant printed circuit boards, polyimide including fluorine resin has low dielectric constant and low coefficient of thermal expansion, and it is necessary to develop polyimide material having high elastic modulus and low moisture absorption. to be.

Prior Art Documents

[Patent literature]

(Patent Document 1) (Preceding Document 001) US Patent No. 4816516

(Patent Document 2) (Prior Document 002) United States Patent No. 7026032

[Contents of the Invention]

Problem to be solved

The present invention is to provide a flexible metal laminate having a low dielectric constant and a low water absorption, while ensuring an optimized coefficient of thermal expansion with high elasticity. [Measures of problem]

The present invention includes a polymer resin layer including a polyimide resin and a fluorine-based resin including a repeating unit represented by Formula 1 below, and the fluorine-based resin is distributed more in the polymer resin layer than in the surface of the polymer resin layer. It provides a flexible metal laminate.

In Formula 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. According to one embodiment of the invention, a polyimide resin comprising a repeating unit of Formula 1 and a polymer resin layer comprising a fluorine-based resin, wherein the fluorine-based resin than the surface of the polymer resin layer inside the polymer resin layer More ductile metal laminates can be provided.

Previously, a method of adding a fluorine-based polymer resin in order to lower the dielectric constant of a polymer resin such as plyimide applied to a flexible metal laminate is known, but polytetrafluoroethylene (PTFE) and tetrafluoroethylene-nucleus, which are representative fluorine-based resins, are known. The thermal expansion coefficients of fluoropropylene copolymer (FEP) and perfluoroalkoxy (PFA) are 135ppm, 150ppm and 230ppm, respectively, which are considerably larger than those of 10 to 30ppm, which is the coefficient of thermal expansion of conventional polyimides. In order to lower the amount of fluorine resin as described above, it is necessary to add about 10 to 60 wt. Accordingly, the present inventors conducted a related research, wherein the flexible metal laminate of the embodiment includes a polymer resin layer containing a polyimide resin and a fluorine resin having the specific chemical structure, and the fluorine resin is outside the polymer resin layer. As a result of more distribution on the inside than the surface, experiments confirmed that an optimized coefficient of thermal expansion with high elasticity and a low dielectric constant and low moisture absorption was obtained through experiments.

As described above, in the polymer resin layer included in the flexible metal laminate, the fluorine resin may be more dispersed in the polymer resin layer than the outer surface of the polymer resin layer, and the content of the fluorine resin may be It may become larger toward the inside of the polymer resin layer.

Specifically, the flexible metal laminated in the body, up to 20% of the thickness from the surface of the polymer resin, the amount of the fluorine-based resin per unit volume of the polymer resin can be ^"increases with depth.

In addition, the content of the fluorine resin per unit volume of the polymer resin layer may be minimum on the surface of the polymer resin layer.

For example, the content of the fluorine resin contained in a unit volume (for example, a cube having a depth at one corner) from a surface of the polymer resin layer to a depth of 1% of the total thickness is 1 of the total thickness. It may be smaller than the amount of fluorine resin per unit volume in the interior deeper than% depth.

In addition, as described above, the content of the fluorine-based resin per unit volume on the surface of the polymer resin layer is minimal, and the content of the fluorine-based resin per unit volume may be increased up to 20% of the total thickness from the surface of the polymer resin layer.

In addition, the fluorine resin content may increase from the surface of the polymer resin layer to 20% of the total thickness, and the fluorine resin content may increase toward the inside from 20% to 50> of the total thickness from the polymer layer resin surface. It may be maintained at the same level as the content of the fluorine resin at a depth point of 20% of the total thickness.

The total content of the fluorine-based resin in the polymer resin layer As the thickness increases to 20%, the weight ratio of the polyimide resin and the fluorine resin per unit volume of the polymer resin layer may vary depending on the depth.

Specifically, at a depth of 20% of the total thickness from the surface of the polymer resin layer, the weight ratio of the polyimide resin: fluorine-based resin per unit volume of the polymer resin layer may be 100: 0 to 60:40.

In addition, at a depth of 40 to 60% of the total thickness of the polymer resin layer, the weight ratio of the plyimide resin: the fluorine-based resin per unit volume of the polymer resin layer may be 80:20 to 30:70.

As such, the fluorine-based resin is more distributed in the polymer resin than the outer surface of the polymer resin layer, or the content of the fluorine-based resin is increased toward the inside of the polymer resin, or the content of the fluorine-based resin per unit volume of the polymer resin. As the minimum on the surface of the polymer resin, the effect of the fluorine-based resin contained in the polymer resin layer, for example, the effect of significantly lowering the dielectric constant and moisture absorption rate can be expressed fully, while the fluorine-based resin Due to this, it is possible to minimize the phenomenon that the thermal expansion coefficient of the polymer resin layer is increased or the elasticity is lowered.

In addition, according to the distribution of the fluorine-based resin, the polymer resin layer may be more firmly bonded to the metal thin film included in the flexible metal laminate, and may be further bonded to at least one surface of the polymer resin layer. The difference in the coefficient of thermal expansion of the polymer resin layer (for example, the second or crab polyimide layer) can be greatly reduced.

In addition, as the fluorine-based resin is more distributed in the polymer resin layer than the surface of the polymer resin layer, the high temperature that can be applied in the manufacturing process of the flexible metal laminate or printed circuit board, for example, application The phenomenon that the fluorine resin melts or the copper foil circuit peels from the insulator can be prevented at a temperature of about 380 ^° C.

On the other hand, the characteristics of the flexible metal laminate of one embodiment described above In addition to the distribution properties of the fluorine-based resin in the polymer layer seems to be due to using a polyimide resin having a specific chemical structure.

Specifically, the polyimide resin including the repeating unit of Formula 1 may include a tetravalent functional group selected from the group consisting of the following Formulas 21 to 27.

[Formula 21]

In Formula 22, ^ is a single bond, -0-, -CO-, -S-, -S0 _2- , -C (C¾) _2- , -C (CF ₃ ) _2- , -C0NH-, -C00 _{_{-, - (CH 2) n}}厂, - 0 (CH 2) n2 0-, or - 0C0 (C¾) 0C0- and _n3, wherein nl, n2 and n3 is an integer of 1 to 10, respectively.

[Formula 23]

In Formula 23, Υ ₂ and Υ ₃ may be the same as or different from each other, a single bond, ᅳ 0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C0NH ᅳ ， -C00-,-

(CH ₂ ) 'i-, -0 (CH ₂ ) _n ₂ 0-, or -0C0 (C¾) _n3 0C0-, wherein nl, n2 and η3 are each an integer from 1 to 10.

[Formula 24]

In Formula 24, Y ₄ , Υ ₅ and Υ ₆ may be the same as or different from each other, each of a single bond, -0-, -CO-, -S-, -S0 _2- , — C (C¾) _2- , _{_{-C (CF 3) 2 -,}} -C0NH-, - C00-, - (CH 2) nl -, -0 (CH 2) _n2 is 0-, or -0C0 (CH ₂₎ _n3 0C0-, wherein nl, n2 and n3 are the integers of 1-10, respectively.

[Formula 25]

In Chemical Formulas 21 to 27, means a bonding point (bonding point). In addition, in order to secure an optimized coefficient of thermal expansion with high elasticity while having a lower dielectric constant and a low water absorption rate of the flexible metal laminate of the embodiment, tetravalent selected from the group consisting of the following Chemical Formulas 28 to 30 It is preferably a functional group. ^ May be the same as or different from each repeating unit of Formula 1.

[Formula 28]

[Formula 29]

[Formula 30]

In Chemical Formulas 28 to 30, means a bonding point (bonding point).

Meanwhile, in Chemical Formula 1, X may be a divalent functional group selected from the group consisting of Chemical Formulas 31 to 34.

In Chemical Formula 31, ¾ is hydrogen, -CH ₃ , -C¾CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ ,-CF ₂ CF ₃₎ -CF2CF2CF3, or -CF ₂ CF ₂ CF ₂ CF ₃ Can be.

[Formula 32]

In Chemical Formula 32, is a single bond, -0-, -C0-, —S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ —, -C0NH-, -C00 _{_{-, - (CH 2) nl}} -, -0 (C¾) n2 0-, -0CH 2 -C (CH 3) 2 - CH2O- or |? 00 (CH ₂₎ _n3 and 0C0-, wherein nl, n2 and n3 is an integer of 1 to 10, respectively, ¾ and ¾ may be the same or different from each other, and hydrogen, -CH ₃ , -CH ₂ C¾, -CH ₂ CH ₂ C¾CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ .

[Formula 33]

In Chemical Formula 33, L ₂ and L ₃ may be the same as or different from each other, and each single bond, -0—, -CO—, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C0NH-, -C00-,-(CH ₂ ) _n厂, -0 (C¾) _n2 0—, -0CH ₂ -C (CH ₃ ) ₂ -CH ₂ 0- or -0C0 (CH ₂ ) _n3 0C ()-, nl, n2 and n3 are each an integer of 1 to 10, R ₂ and ¾ may be the same or different from each other, hydrogen,-(¾, -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 .

[Formula 34]

In Formula 34, L ₄ , L _5, and L ₆ may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C0NH ᅳ, -C00-,-(CH ₂ ) _n厂, -0 (CH ₂ ) _n2 0—, -0CH ₂ -C (CH ₃ ) ₂ -CH ₂ 0 Or -0C0 (C¾) _n3 0C0-, nl, n2 and n3 are each an integer of 1 to 10, ¾ and R4 may be the same or different from each other, hydrogen, -CH ₃ , -CH ₂ CH ₃ ,- It may be _{_{_{CF 2 CF 3, -CF 2 CF}}} 2 CF 3, or _{_{_{_{-CF 2 CF 2 CF 2 CF 3}}}} - CH 2 CH 2 CH 2 CH 3, -CF 3,.

In particular, when X in Chemical Formula 1 is a divalent functional group in Chemical Formula 35, the flexible metal laminate of the embodiment may have a lower dielectric constant and a lower water absorption rate, and may also secure an optimized coefficient of thermal expansion with high elasticity. have. X may be the same as or different from each repeating unit of Formula 1.

[Formula 35]

In Formula 35, and R ₂ may be the same as or different from each other, and-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 .

On the other hand, the polymer resin layer may include a polyimide resin 20 to 95 weight ¾> or 40 to 90 weight and the remaining amount of the fluorine-based resin comprising a repeating unit of the formula (1). If the content of the fluorine-based resin is too small, the resulting soft metal laminate may not be able to secure a sufficiently low dielectric constant or moisture absorption rate. In addition, if the content of the fluorine-based resin is too large, the mechanical properties of the flexible metal laminate is lowered and easily torn or broken The thermal expansion coefficient of the polymer resin layer included in the flexible metal laminate may be greatly increased.

The fluororesin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-nuclear fluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer It includes a fluoropolymer containing at least one selected from the group consisting of a polymer resin (ETFE), tetrafluoroethylene- chlorotrifluoroethylene copolymer (TFE / CTFE) and ethylene- chlorotrifluoroethylene resin (ECTFE) can do.

The fluorine-based resin may include particles having a longest diameter of 0.05 Urn to 20, or 0.1 to 10 to 10. If the longest diameter of the fluorine-based resin is too small, the surface area of the fluorine-based resin may increase to decrease the physical properties of the polymer resin layer or increase the amount of the dispersant to be described later. In addition, when the longest diameter of the fluorine-based resin is too large, the surface properties of the polymer resin layer to be produced may be lowered or the dispersibility of the polymer composition solution for producing the polymer resin layer may be lowered.

Meanwhile, the flexible metal laminate of the embodiment may further include a dispersant dispersed in the polymer resin layer.

The polymer resin layer may be formed from a resin composition comprising a polyamic acid, a fluorine resin, and a predetermined dispersant, and as the dispersant is used, the fluorine resin is more distributed in the polymer resin than the outer surface of the polymer resin layer. Alternatively, the content of the fluorine resin may be increased toward the inside of the polymer resin layer, or the content of the fluorine resin per unit volume of the polymer resin layer may be minimum on the surface of the polymer layer resin.

Specific examples of the dispersant include polyester-based polymers, polyether-modified polydimethylsiloxanes, polyester / polyamine condensation polymers or two or more kinds thereof. The ^'according to the use of such compounds, may be a fluorine-based resin is the above-described distribution pattern in the number of the polymer resin contained in the flexible laminated body, whereby the depending Flexible metal laminates or printed circuit boards may have an optimized coefficient of thermal expansion with high elasticity while having low dielectric constant and low moisture absorption.

Previously, a method of using a fluorine-based dispersant or a fluorine-based surfactant in order to disperse the fluorine-based resin in polyamic acid or polyimide is known, but according to the conventional method, the dielectric constant of the polymer resin layer manufactured may be somewhat lowered. The coefficient of thermal expansion of the polymer resin layer prepared according to the use of the agent or the fluorine-based surfactant may be greatly increased.

In addition, when the fluorine-based dispersant or the fluorine-based surfactant is used, a phenomenon in which the fluorine-based resin is concentrated on the surface of the polymer resin layer, such as a polyimide resin, to be produced, may occur. Exposure to high temperatures that may be applied in the manufacture of sieves or printed circuit boards, for example around 380 ^o C, may cause the fluorine resin to melt or to exfoliate portions of the flexible metal laminate or printed circuit board. have.

Previously, a method of adding a fluorine-based polymer resin in order to lower the dielectric constant of a polymer resin such as polyimide applied to a flexible metal laminate is known. However, polytetrafluoroethylene (PTFE) and tetrafluoroethylene-nucleofluoride, which are representative fluorine resins The thermal expansion coefficients of propylene copolymer (FEP) and perfluoroalkoxy (PFA) are 135ppm, 150ppm and 230ppm, respectively, which are considerably larger than those of 10 to 30ppm, which is the coefficient of thermal expansion of conventional polyimides. In order to lower the amount of the fluorine resin as described above 10 to 60wt%, the overall coefficient of thermal expansion is bound to increase.

The dispersant is 0.92 g / ml to 1.2 g / ml, or 0.95 g / ml at 20 ^o C

It may have a density of 1.15 g / ml.

The dispersant may have an acid value (Ac id value) of 20 to 30 mg KOH / g.

In addition, the dispersant has a base equivalent of 1000 to 1700 Can have.

The polymer resin layer may include 0.1 parts by weight to 25 parts by weight or 0.5 parts by weight to 10 parts by weight of the dispersant relative to 100 parts by weight of the fluorine resin.

If the content of the dispersing agent- is too small, the fluorine-based resin agglomeration may occur to reduce the appearance characteristics or uniformity of the polymer resin layer, uniformity of the polymer resin composition solution for the production of the polymer resin layer Can be lowered. In addition, when the content of the dispersant is too large, the elasticity or mechanical properties of the polymer resin layer may be lowered.

On the other hand, the polymer resin layer included in the flexible metal laminate may have a thickness of 0.1zm to 100 / 皿, or 1 / 皿 to 50.

The flexible metal laminate may exhibit a dielectric constant (Dk) of 2.2 to 2.8, or 2.3 to 2.7 in a dry state at 5 GHz. In general, the polyimide resin has a dielectric constant of 3.0 or more in a dry state at 5 GHz, whereas the flexible laminated metal laminate of the embodiment may have a relatively low dielectric constant as described above with the polymer resin layer. The flexible laminated body may have a coefficient of thermal expansion of lppm to 28ppm at 100 ° C to 200 ^o C.

The polymer resin layer described above may have a relatively low coefficient of thermal expansion, for example, lppm to 20 ppm, and a flexible metal including the polymer resin layer or an additional polyimide layer on at least one surface of the polymer resin layer. The laminate may also have a coefficient of thermal expansion of lppm to 28 ppm, or 15 ppm to 25 ppm.

Since the thermal expansion coefficient of copper foil, which is a commonly used metal foil, is about 18 ppm, the thermal expansion coefficient of the flexible metal laminate should be within the above-described range, so that warpage phenomenon resulting from the difference in thermal expansion coefficient with the metal foil can be minimized. Minimize the difference in expansion and contraction with other materials forming the printed circuit board.

On the other hand, the flexible metal laminate is copper, iron, nickel, titanium, aluminum, At least one metal thin film including at least one selected from the group consisting of silver, gold and two or more alloys thereof may be included.

Specifically, the flexible metal laminate may include one metal thin film, and the flexible metal laminate may include two metal thin films that face each other, and in this case, the polymer resin layer may face each other. It may be located between two metal thin film.

Ten-point average roughness (R _Z ) of the surface of the metal thin film may be 0. 3 to 2.5Λΐι. If the ten point average roughness of the metal thin film surface is too small, the adhesive strength with the polymer resin layer may be low, and if the ten point average roughness of the metal thin film surface is too large, the surface roughness may increase to increase the transmission loss in the high frequency region.

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

The flexible metal laminate described above may further include a polyimide resin layer formed on at least one surface of the polymer resin layer.

Specifically, the flexible metal laminate may further include second and third polyimide resins bonded to both sides of the polymer resin layer. The second and third polyimide resins may each have the same or different composition as the above-described polyimide resin.

In addition, the second and third polyimide resin may have the same or different thickness as the polymer resin layer, and may have a thickness in the range of 0.1 to 100 / 皿, or to 50 / 皿.

In addition, the manufacturing method of the above-mentioned flexible metal laminated body is not restrict | limited significantly, Usually, the synthesis | combining method of a known polyimide resin, and the manufacturing method of a flexible metal laminated body can be used.

The polyimide resin included in the polymer resin layer may be obtained by heat treatment at a high temperature of 250 ^° C. to 400 ^° C. after coating and drying a polymer resin solution including a polyamic acid as a precursor.

In addition, the polyamic acid as a precursor of the polyimide resin reacts with tetracarboxylic acid or its anhydride and diamine compound. A diamine comprising a tetracarboxylic acid or an anhydride thereof including a tetravalent functional group selected from the group consisting of Formula 21 to Formula 27 and a divalent functional group selected from the group consisting of Formulas 31 to 34, for example. By reacting the compounds.

The resin composition including a polyamic acid, a fluorine resin, and a dispersant, which is a precursor of the polyimide, may include an organic solvent, and examples of the organic solvent that can be used are not particularly limited. For example, N, N′-dimethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N, N'-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 1, 3- Dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxydi, dimethulfone, m-cresol, P- Chlorophenol, anisol, etc. may be used, and may be used alone or in combination of two or more. At this time, the usable amount of the organic solvent may use about 2 to 8 times the total solids of the resin composition.

【Effects of the Invention】

According to the present invention, there can be provided a flexible metal laminate having a low dielectric constant and a low water absorption rate, while ensuring an optimized coefficient of thermal expansion with high elasticity.

Accordingly, the present invention is a solution to the increase in the data loss rate, the thickening of the printed circuit board, the narrowing of the circuit on the printed circuit board caused by the recent increase in data transmission speed of devices such as laptops, computers, mobile phones As a method, there is provided a method capable of producing a low dielectric constant polyimide having a low dielectric constant and having characteristics such as high heat resistance chemical resistance and dimensional stability of an existing polyimide insulator.

In addition, the present invention provides a method capable of producing a low dielectric constant copper foil laminate using a low dielectric constant polyimide prepared according to the above method. As a result, the printed circuit board can be made thinner while matching impedance, thereby making the portable electronic device thinner, and the line width of the printed circuit board can be widened, thereby significantly reducing the defect rate of the PCB manufacturing company. It can greatly contribute to cost reduction. [Brief Description of Drawings]

Figure 1 shows a cross-sectional SEM photograph and EDS results of the copper foil laminate obtained in Example 8.

FIG. 2 is an enlarged cross-sectional SEM photograph of the laminate of FIG. 1.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. Preparation Example: Preparation of Polyamic Acid Solution

Preparation Example 1 Preparation of Polyamic Acid Solution Containing Fluorine Resin (P1)

Nitrogen was charged in a 1 L PE bottle, 765 g of dimethylacetamide (DMAc), 219 g polytetra pulluloethylene micro powder (PTFE micro powder, particle size: 0.1 to 2.0 um), and poly with dispersant. 10.95 g of ester polymer [acid value 26 mg KOH / g, base value 1200] and 765 g of beads having a diameter of 2 mm were added thereto, and PTFE was dispersed while stirring in a high speed ball milling machine. .

80 g dimethylacetamide 107 g, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride 1.852 g, pyromellitic dianhydride 12.355 g, 2 ， 2'-dimethyl-4,4'-diaminobiphenyl 5.453g, 2,2'-bis (trifluoromethyl) -4，4'-diaminobiphenyl 12.340g was added, at 50 ° C.

The reaction mixture was stirred with a stirrer while flowing nitrogen for 10 hours to obtain a polyamic acid solution (P1) having a viscosity of about 25,000 cps. Preparation Example 2 Preparation of Polyamic Acid Solution Containing Fluorine Resin (P2)

11 »layered nitrogen in a PE bottle, 765 g of dimethylacetamide (DMAc), polytetrafluoroethylene micro powder, particle size: 0.1 to 2.0um) 219g, 10.95g of polyester polymer [acid value 26 mg KOH / g, base value 1200] and 2mm diameter bead 765g as a dispersant, PTFE was added while stirring in a high speed ball milling machine. Dispersed.

The PTFE was dispersed in a 500 mL back bottom flask. 73 g of solution 73 g dimethylacetamide, 11.609 g pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl 17.391g, at 50 ° C

The reaction was carried out using a stirrer while flowing nitrogen for 10 hours to obtain a polyamic acid solution (P2) having a viscosity of about 100,000 cps. Preparation Example 3 Preparation of Polyamic Acid Solution Containing Fluorine Resin (P3)

1 L of PE bottle was filled with nitrogen, 765 g of dimethylacetamide (DMAc), 219 g of polytetrafluoroethylene micro powder (particle size: 0.1 to 2.0 um), polyester with dispersant 10.95 g of a system polymer (density (20): 1.13 g / ml) and 765 g of beads having a diameter of 2 mm were added thereto, and PTFE was dispersed while stirring in a high speed ball milling machine.

107 g of 80 g dimethylacetamide in which a solution of PTFE was dispersed in a 500 mL back bottom flask, 13.937 g pyromellitic dianhydride, 2,2'-dimethyl 4,4'-diaminobiphenyl (2,2'—dimethyl- 4,4'-diamino bihenyl, m-TB-HG) 5.536 g, 2,2'-bis (trifluoromethyl) ᅳ 4,4'-diaminobiphenyl

12.527 g was added and reacted with stirring using a stirrer while flowing nitrogen at 50 ^° C. for 10 hours to obtain a polyamic acid solution (P3) having a viscosity of about 20,000 cps. Preparation Example 4 Preparation of Polyamic Acid Solution (P4)

187g of dimethylacetamide (DMAc), 12.355g of pyromellitic di anhydride (PMDA) in 500mL back-bottom flask, 3,4，3 ', 4'- Biphenyltetracarboxylic dianhydride (BPDA) 1.852g, 2, 2'-dimethyl-4,4'—diaminobiphenyl (2,2'-dimethyl-4,4'_ diamino bihenyl, m- TB-HG)

5.453 g, 2,2'-bis (trifluoromethyl) -4,4 'ᅳ diaminobiphenyl (2,2'-TFDB)

12.340 g was added and reacted with stirring using a stirrer while blowing nitrogen at 50 ^° C. for 10 hours to obtain a polyamic acid solution (P4) having a viscosity of about 20,000 cps. Preparation Example 5 Preparation of Polyamic Acid Solution (P5)

200 g of dimethylacetamide (DMAc), pyromellitic di anhydride (PMDA) lO.OOg, in a 500 mL back-bottom flask

18.82 g of ([aminophenoxy] -phenyl) propane (BAPP) was added, and the reaction mixture was stirred using a stirrer while nitrogen was poured at 50 ° C. for 10 hours, and a plymic acid solution having a viscosity of about 5,000 cps. (P5) was obtained. Preparation Example 6 Preparation of Polyamic Acid Solution (P6)

Dimethylacetamide (DMAc) 200 g, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride (BPDA) 26.65 g, p-phenylene diamine (PDA) in a 500 mL back bottom flask 9.98 g was added and reacted with stirring using a stirrer while flowing nitrogen at 50 ° C. for 10 hours to obtain a polyamic acid solution (P6) having a viscosity of about 5,000 cps. Preparation Example 7 Preparation of Polyamic Acid Solution Containing Fluorine Resin (P7)

1 L of PE bottle was filled with nitrogen, 765 g of dimethylacetamide (DMAc), 219 g of polytetrafluoroethylene micro powder (PTFE micro powder, particle size: 0.1 to 2.0 um), polyester with dispersant Type Polymer [acid value 26 mg K0H / g, base value 10.95 g and 765 g of beads having a diameter of 2 mm were added, and PTFE was dispersed while stirring in a high speed ball milling machine.

Dimethylacetamide (DMAc) 112 g, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride (BPDA) 21.817 g, p in a solution of PTFE dispersed in a 500 mL round bottom flask 7 8.183 g of -phenylene diamine (PDA) was added thereto, and the reaction mixture was stirred with a stirrer while giving nitrogen at 50 ° C. for 10 hours to obtain a polyamic acid solution (P7) having a viscosity of about 35,000 cps. [Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of Polyimide Resin Film for Flexible Metal Laminate]

Examples 1 to 3

The polyamic acid solutions prepared in Preparation Examples 1 to 3 were coated on a Matte surface of copper foil (thickness: 12) so that the final thickness was 25 μm, and then dried at 80 ° C. for 10 minutes. The dried product was started at room temperature in a nitrogen oven to proceed with curing at 350 ° C. for 30 minutes. After the curing was completed, the copper foil was etched to prepare a polyimide film having a thickness of 25 μm. Example 4

Instead of the polyamic acid solution (P1) prepared in Preparation Example 1, except that the polyamic acid solution (P7) prepared in Preparation Example 7 was used, a plyimide film having a thickness of 25 μm was prepared in the same manner as in Example 1. Prepared. Comparative Examples 1 to 3

Polyimide having a thickness of 25 μm in the same manner as in Example 1, except that the polyamic acid solution obtained in Preparation Examples 4 to 6 was used instead of the polyamic acid solution prepared in Preparation Examples 1 to 3, respectively. A film was prepared.

[Examples 5 to 10 and Comparative Example 4: Preparation of Flexible Metal Laminate]

Implementation ^] 5

The polyamic acid solution (P5) prepared in Preparation Example 5 was coated on a Matte surface of a copper foil (thickness: i / m) so that the final thickness is 2um and dried at 80 ° C for 10 minutes. The polyamic acid solution (P1) prepared in Preparation Example 1 thereon was coated to a final thickness of 20um and then dried at 80 ° C for 10 minutes. Then, the polyamic acid solution (P1) on the surface of the dried product, the polyamic acid solution (P5) prepared in Preparation Example 5 was coated to a final thickness of 3um and then dried at 80 ° C. for 10 minutes to prepare a laminate. .

The dried laminate was heated at room temperature in a nitrogen oven, and cured at 350 ^° C. for 30 minutes to produce a flexible copper foil laminate having one surface of the copper foil. Examples 6-7

The surface was the same as in Example 5 except for using the polyamic acid solutions (P2 and P3) prepared in Preparation Example 2 and Preparation Example 3 instead of the polyamic acid solution (P1) prepared in Preparation Example 1. The flexible copper foil laminated board which one side is made of copper foil was manufactured. Example 8

The polyamic acid solution (P5) prepared in Preparation Example 5 was coated on a Matte surface of copper foil (thickness: 12zm) so that the final thickness is 2um, and dried at 80 ° C for 10 minutes. The polyamic acid solution (P1) prepared in Preparation Example 1 was coated thereon to have a final thickness of 20 μm, and then dried at 80 ^° C. for 10 minutes. And, on the surface of the dried product of the polyamic acid solution (P1), prepared in Synthesis Example 5 The polyamic acid solution (P5) was coated to a final thickness of 3 μm and then at 80 ^o C

It dried for 10 minutes and manufactured the laminated body.

After drying the dried laminate at room temperature in nitrogen Aubon for 30 minutes at 350 ^o C, the copper foil (thickness: 1 ΛΙΙ) on the other side of the cured product so as to face the copper foil at a temperature of 400 ° C. It bonded by and manufactured the flexible copper foil laminated board which copper foil was bonded to both surfaces. Examples 9-10

Except for using the polyamic acid solution (P2 and P3) prepared in Preparation Example 2 and Preparation Example 3 instead of the polyamic acid solution (P1) prepared in Preparation Example 1, both sides in the same manner as in Example 8 The flexible copper foil laminated board which copper foil was bonded to was manufactured. Example 11

Except for using the polyamic acid solution (P7) prepared in Preparation Example 7 instead of the polyamic acid solution (P1) prepared in Preparation Example 1, the same flexibility as the copper foil on both sides in the same manner as in Example 8 The copper foil laminated board was manufactured. Experimental Example

Experimental Example 1 Observation of the Cross-section of a Soft Metal Red Lump

The cross section of the copper foil crushing plate obtained in the said Example 8 was confirmed through the SEM photograph.

As shown in FIG. 1 and FIG. 2, it was confirmed that fluorine-based resin was more distributed inside the resin than the outer surface in the polyimide resin layer of the flexible metal laminate prepared in Example 8.

In addition, it was confirmed that the fluorine resin content continued to increase from the surface of the polyimide resin layer of the flexible metal laminate to a certain depth, for example, up to about 20% of the total thickness from the surface of the polymer resin layer. 2. Experimental Example 2: Measurement of Physical Properties of Ductile Metal Lumps

Dielectric constant for the copper foil laminate obtained in the above Examples and Comparative Examples,

CTE and water absorption were measured as follows, and the results are shown in Table 1 below.

(1) dielectric constant measurement method

The polyimide film laminate obtained by etching the copper foil in the polyimide film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the flexible copper foil laminate obtained in Examples 4 to 11 was dried at 150 ^° C. for 30 minutes, and The dielectric constant of the polyimide film or the polyimide film laminate was measured using a split post dielectric resonance (SPDR) method at 25 ° C. and 50% RH.

The measurement was performed using a Resonator using an E5071B ENA apparatus.

(2) How to measure the coefficient of thermal expansion (CTE)

The linear thermal expansion coefficients of the polyimide films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the linear thermal expansion coefficients of the polyimide film laminates obtained by etching copper foil from the flexible copper foil laminates obtained in Examples 4 to 11 were obtained from IPC TM-.

650 at 100 ° C to 200 ^° C measurement conditions, based on 2.4.24.3

Measurements were made using a TMA / SDTA 840 instrument from Mettler.

(3) Absorption rate measurement method

The absorption rate of the polyimide film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the absorption rate of the polyimide film laminate obtained by etching copper foil from the flexible copper foil laminates obtained in Examples 4 to 11 were IPC TM-650 2.6.2C It was immersed in distilled water of 23 ⁰ C for 24 hours based on the criterion of, and the water absorption was calculated by measuring the mass of the measurement object before and after the deposition.

Table 1 Measurement Results of Experimental Example 2

* In Table 1, the composition of the polyamic acid of Examples 5 to 11 relates to the precursor of the polyimide film located in the middle layer of the polyimide films of the flexible copper foil laminate. As shown in Table 1, the polyimide film obtained in Examples 1 to 3 has a low dielectric constant and low water absorption, but also in a suitable range (for example, lppm to 20 ppm) as compared to the polyimide films of Comparative Examples 1 to 3. It was confirmed that it has a coefficient of thermal expansion of.

In contrast, it was confirmed that the polyimide films of Comparative Examples 1 to 3 had relatively high dielectric constants (for example, 2.8 or more or 3.0 or more) and high absorption rates (for example, 1.5% or more).

Meanwhile, in the case of the copper foil metal laminates prepared in Examples 5 to 11, the dielectric constant of 2.80 or less and the absorption rate of 1.2 or less can be secured, while the thermal expansion coefficient of the laminated structure excluding copper foil can be adjusted in the range of 18 ppm to 28 ppm. Confirmed.

In particular, when including a polyimide film obtained from a polyamic acid synthesized using a specific monomer (Examples 5 to 10), it is possible to ensure a lower dielectric constant and water absorption while maintaining an appropriate coefficient of thermal expansion. Has been confirmed

Claims

[Patent Claims]

[Claim 1]

To include a polymer resin containing a polyimide resin and a fluorine-based resin comprising a repeating unit of the formula (1),

The fluorine-based resin is more distributed in the interior of the polymer resin layer than the surface of the polymer resin layer, soft metal laminate:

[Formula 1]

In Chemical Formula 1, Yr is a tetravalent aromatic organic functional group, X is a divalent aromatic organic functional group, and n is an integer of 1 to 300.

[Claim 2]

The method of claim 1,

The content of the fluorine-based resin per unit volume of the polymer resin layer increases with depth from the surface of the polymer resin layer to 20% of the total thickness, soft metal laminate.

[Claim 3]

The method of claim 2,

A flexible metal laminate, wherein the content of the fluorine-based resin per unit volume of the polymer resin layer is minimum at the surface of the polymer resin layer.

[Claim 4]

The method of claim 2,

At a depth of 20% of the total thickness from the surface of the polymer resin layer, The flexible metal laminate of claim 1, wherein the weight ratio of the polyimide resin: fluorine-based resin per unit volume of the polymer resin layer is 100: 0 to 60:40.

[Claim 5]

According to claim 2,

And a weight ratio of the polyimide resin: fluorine-based resin per unit volume of the polymer resin layer at a depth of 40 to 60% of the total thickness of the polymer resin layer is 75:25 to 25:75.

[Claim 6]

The method of claim 1,

Yi is a tetravalent functional group selected from the group consisting of Formula 21 to Formula 27, a flexible metal laminate:

[Formula 21]

In Formula 22, is a single bond, -0-, -CO-, -S-, -S0 _2- , -C (C¾) ₂ ᅳ, -C (CF ₃ ) ₂ ᅳ, -C0NH-, -C00- , — (C¾) _nl — ， — 0 ((¾) _η2 0-, or −0C0 (C¾) _n3 0C0-, wherein nl, n2 and n3 are each an integer from 1 to 10,

[Formula 23]

In Formula 23, Y ₂ And Υ _{3 It} may be the same or different from each other, each a single bond, -0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C _{_{(CF 3) 2 -, -C0NH-}} , -C00-, - (C¾) nl -, -0 (CH 2) _n2 is 0-, or ¾00 (C¾) _n3 0C0-, wherein nl, n2 and n3 are each An integer of 1 to 10,

In Formula 24, Υ ₄ , Υ ₅ and Υ ₆ may be the same as or different from each other, each a single bond, -0-, -C0-, ᅳ S-, -S0 _2- , -C (C¾) _2- , -C (CF ₃ ) ₂ —, -C0NH-, -C00-,-(CH ₂ ) ni-, -0 (CH ₂ ) _n2 0-, or -0C0 (C¾) _n3 0 ⁽ D-, wherein nl , n2 and n3 are each an integer of 1 to 10,

[Formula 25]

[Formula 26]

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

[Claim 7]

The method of claim 1,

The ^ is a tetravalent functional group selected from the group consisting of Formulas 28 to 30, a flexible metal laminate:

[Formula 28]

[Formula 30]

In Chemical Formulas 28 to 30, means a bonding point (bonding point).

[Claim 8]

The method of claim 1,

X is selected from the group consisting of

Functional group, flexible metal laminate:

[Formula 31]

In Formula 31, Rr hydrogen,-(¾, -CH ₂ CH ₃ , -CH ₂ CH ₂ C¾CH ₃ , -CF ₃ , CF ₂ CF ₃ , -CF ₂ CF ₂ CF _3> or -CF ₂ CF ₂ CF ₂ CF ₃ ,

[Formula 32]

In Chemical Formula 32, is a single bond, -0-, -co-, -s-, -so _2- , -C (C¾) _2- , -C (CF ₃ ) _2- , -C0NH-, -C00- _{, - (C¾) nl -,} -0 (CH 2) n2 0-, -0CH 2 -C (CH 3) 2 - CH 2 0- or ¾ | 00 (CH ₂₎ _n3 and 0C0-, wherein nl, n2 And n3 are each an integer of 1 to 10, ¾ and R ₂ may be the same or different from each other, hydrogen, ， C¾, —CH ₂ CH; -CH ₂ C¾CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃₎ -CF ₂ CF ₂ CF ₃₎ or — CF ₂ CF ₂ CF ₂ CF ₃ ,

[Formula 33]

In Formula 33, L ₂ and L ₃ may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ - ₍ -C0NH-, -C00-,-(CH ₂ ) ni-, -0 (C¾) _n2 0-, -0CH ₂ -C (CH ₃ ) 2-CH ₂ 0- or ᅵ! and 00 (CH ₂₎ _n3 0C0-, and wherein nl, n2 and n3 is an integer from 1 to 10,

Ri, ¾ and R ₃ may be the same or different from each other, and hydrogen, -CH ₃ ,-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ C¾, -CF ₃₎ -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ ,

[Formula 34]

In Formula 34, L ₄ , L ₅ and L ₆ may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , — C0NH-,-C00-,-(CH ₂ ) _n i-, -0 (CH ₂ ) _n2 0-, -0CH ₂ -C (CH ₃ ) 2-CH ₂ 0- or ¾ 00 (C¾) _n3 0C ()-, wherein nl, n2 and n3 are each an integer of 1 to 10,

Ri, ¾ and ¾ may be the same or different from each other, and hydrogen, — (¾,-CH ₂ CH ₃ , -C¾CH 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 , in Chemical Formulas 31 to 34, denotes a bonding point.

[Claim 9] In U,

X is a divalent functional group represented by Chemical Formula 35

Genus laminate:

[Formula 35]

In Formula 35, and ¾ may be the same or different from each other, -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 .

[Claim 10]

The method of claim 1,

Further comprising a dispersant dispersed in the polymer resin layer

^ Stacks.

[Claim 11]

The method of claim 10,

The dispersant comprises at least one selected from the group consisting of polyester polymers, polyether modified polydimethylsiloxane and polyester / polyamine polymer, soft metal laminate. [Claim 12]

The method of claim 10,

Said dispersant having a density of from 0.92 g / ml to 1.2 g / ml at 20 ^° C .; [Claim 13]

Clause 10 The dispersant is a flexible metal laminate having an acid value of 20 to 30 mg KOH / g or a base equivalent of 1000 to 1700.

[Claim 14]

The method of claim 10,

The flexible metal laminate of the polymer resin layer comprises 0.1 parts by weight to 25 parts by weight of the dispersant relative to 100 parts by weight of the fluorine-based resin.

[Claim 15]

The method of claim 1,

The fluororesin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer Polymer resin (ETFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE) _. And at least one selected from the group consisting of ethylene-chlorotrifluoroethylene resin (ECTFE).

[Claim 16]

The method of claim 1,

Said fluorine-type resin contains the particle | grains which have the longest diameter of 0.05-20, The flexible metal laminated body.

[Claim 17]

According to claim 1,

The polymer resin layer comprises 20 to 95% by weight of a polyimide resin containing a repeating unit of the formula (1) and a residual amount of fluorine-based resin, flexible metal laminate. [Claim 18] The method of claim 1,

The polymer resin layer has a thickness of 0.1 to 100 / m, flexible metal laminate. [Claim 19]

The method of claim 1,

The soft metal antagonist of the dielectric constant of the polymer resin layer at 5 GHz is 2.2 to 2.8. [Claim 20]

According to claim 1,

From 100 ° C to about 200 ^o C with a thermal expansion coefficient of lppm to 28ppm, the flexible metal laminate. [Claim 21]

The method of claim 1,

A flexible metal laminate comprising at least one metal thin film comprising at least one selected from the group consisting of copper, iron, nickel, titanium, aluminum, silver, gold and two or more alloys thereof.

[Claim 22]

The method of claim 21,

The ten point average roughness (Rz) of the said metal thin film surface is 0.5 / im, The flexible metal laminated body.

[Claim 23]

The method of claim 21,

The metal thin film has a thickness of 0.1 / 50 / m, flexible metal laminate. [Claim 24]

The method of claim 21,

It includes two of the metal thin film facing each other,

A flexible metal laminate, wherein the polymer resin layer is positioned between two metal thin films opposing each other.

[Claim 25]

The method of claim 1,

The flexible metal laminate further comprising a polyimide resin layer formed on at least one surface of the polymer resin layer.

[Claim 26]

The method of claim 25,

The polyimide resin layer has a thickness of 1 to 50; mi, flexible metal laminate.