KR102065643B1 - Flexible Copper Clad Layer and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a flexible copper foil laminated film and a method for manufacturing the same, and more particularly, to a flexible copper foil laminated film having a thin thickness and excellent peel strength, tensile strength, elastic modulus, elongation, moisture absorption and heat resistance, and a method of manufacturing the same. It is about.

Description

Flexible Copper Clad Lamination Film and Manufacturing Method Thereof {Flexible Copper Clad Layer and manufacturing method}

The present invention relates to a flexible copper foil laminated film and a method for manufacturing the same, and more particularly, to a flexible copper foil laminated film having a thin thickness and excellent peel strength, tensile strength, elastic modulus, elongation, moisture absorption and heat resistance, and a method of manufacturing the same. It is about.

Printed circuit board (PCB) is a representation of the electrical wiring to connect the various parts according to the circuit design according to the circuit design and serves to connect or support the various components. In particular, with the development of electronic devices such as notebook computers, mobile phones, PDAs, small video cameras and electronic organizers, the demand for printed circuit boards has increased. Furthermore, the electronic devices are becoming smaller and lighter, with the emphasis on portability. Therefore, printed circuit boards are becoming more integrated, smaller, and lighter.

The printed circuit board may be a multi-flexible substrate similar to a rigid printed circuit board, a flexible printed circuit board, a rigid-flexible printed circuit board, a rigid-flexible printed circuit board, and a rigid-flexible printed circuit board. It is divided into a printed circuit board. In particular, flexible copper clad layer (FCCL), a raw material for flexible printed circuit boards, is used in digital home appliances such as mobile phones, digital camcorders, laptops, and LCD monitors. Demand is growing rapidly.

Flexible copper foil laminated | multilayer film laminated | stacked the polymer film layer and the metal conductive layer, and is characterized by having flexibility. Flexible copper foil laminated films are particularly used for electronic devices or material parts of electronic devices that require flexibility and flexibility, and contribute to miniaturization and light weight of electronic devices.

Conventional flexible copper foil laminated films associated with this technology are largely divided into a method of applying a polyimide resin to the copper foil and a method of depositing copper on the polymer film. In particular, the copper deposition method can form a very thin copper film.

A flexible copper foil laminated film of a deposition method is prepared by forming a tie-coat layer on a polymer film by sputtering, and then electroplating copper while continuously passing it through a copper electrolytic plating bath.

The fabricated flexible copper foil laminated film is a semiconductor chip or an electric element mounted on the circuit after circuit formation, and is used in a miniaturized, multi-pinned, narrow pitch of a driver IC. . Accordingly, there is a need for a flexible copper foil laminated film having a thin thickness and excellent physical properties such as excellent peel strength, tensile strength, elastic modulus, elongation, and moisture absorption rate.

However, currently produced flexible copper foil laminated film has a problem that does not meet the required physical properties.

Korea Patent Registration No. 10-1421701 (Publish Date: 2014.04.04)

The present invention has been made in view of the above, and an object thereof is to provide a flexible copper foil laminated film having a thin thickness and excellent peel strength, tensile strength, elastic modulus, elongation, hygroscopicity and heat resistance, and a method of manufacturing the same. .

In order to solve the above problems, the flexible copper foil laminated film of the present invention includes a polyimide substrate layer, a metal plating layer formed on one surface or both sides of the polyimide substrate layer and a copper foil layer formed on one surface of the metal plating layer, the polyimide substrate The layer includes a first polyimide substrate layer and a second polyimide substrate layer formed on one or both surfaces of the first polyimide substrate layer, wherein the first polyimide substrate layer contains amorphous calcium phosphate having an average particle diameter of 1 to 7 μm. The second polyimide base layer may include spherical silica having an average particle diameter of 50 to 250 nm.

In a preferred embodiment of the present invention, the first polyimide base layer contains 1% by weight or less of calcium phosphate in the total weight, and the second polyimide base layer has 0.5 to 5 weight parts of silica in the total weight. May contain%.

As a preferred embodiment of the present invention, the silica of the second polyimide base layer may satisfy both the following conditions (1) and (2).

≤ 4.34(1) 2.88 ≤

≤ 4.34

(2) 19.4 nm ≤ D10 ≤ 29.3 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, 444.8 nm ≤ D90 ≤ 667.2 nm

In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.

As a preferred embodiment of the present invention, the second polyimide substrate layer is a compound represented by the following formula (1), a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), The compound represented by the formula (5), the compound represented by the formula (6) and the compound represented by the formula (7) may further include an imidization reaction of the polyamic acid polymerized.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 5, R ₁ and R ₂ are each independently -H or an alkyl group of C1 to C5,

[Formula 6]

In Formula 6, R ₃ and R ₄ are each independently, an alkylene group of C1 ~ C7, R ₅ , R ₆ , R ₇ and R ₈ are each independently -H or an alkyl group of C1 ~ C5,

[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently -H or C1 ~ It is an alkyl group of C5, n is a free number which is 1-20.

As a preferred embodiment of the present invention, the polyamic acid is 94.9 to 142.5 parts by weight of the compound represented by Formula 2, 30.0 to 38.0 parts by weight of the compound represented by Formula 3, based on 100 parts by weight of the compound represented by Formula 1 6.8 to 10.3 parts by weight of the compound represented by 4, 17.2 to 26.0 parts by weight of the compound represented by Formula 5, 8.3 to 12.6 parts by weight of the compound represented by Formula 6, and 7.1 to 10.8 parts by weight of the compound represented by Formula 7 Can be.

As a preferred embodiment of the present invention, the compound represented by Chemical Formula 6 and the compound represented by Chemical Formula 7 may include 1: 0.68 to 1.03 by weight.

In a preferred embodiment of the present invention, the polyimide substrate layer may have a thickness ratio of 1: 0.12 to 0.19 for the first polyimide substrate layer and the second polyimide substrate layer.

In one preferred embodiment of the present invention, the first polyimide substrate layer is a compound represented by the formula (4), a compound represented by the formula (8), a compound represented by the formula (9) and a compound represented by the formula (10) It may comprise an imidization reaction of the polyamic acid.

[Formula 8]

[Formula 9]

[Formula 10]

In a preferred embodiment of the present invention, the metal plating layer includes a first metal plating layer formed on one surface of the second polyimide substrate layer and a second metal plating layer formed on one surface of the first metal plating layer, wherein the first metal plating layer is Nickel or a nickel-copper alloy may be included, and the second metal plating layer may include copper.

As a preferred embodiment of the present invention, the metal plating layer may have a thickness ratio of 1: 4.8 to 7.2 of the first metal plating layer and the second metal plating layer.

On the other hand, the method for producing a flexible copper foil laminated film of the present invention is a first step of preparing a polyamic acid solution containing an inorganic filler, a second step of applying a polyamic acid solution to one or both sides of the polyimide substrate to produce a polyimide substrate A third step of forming a metal plating layer by sputtering process on one or both sides of the polyimide substrate layer and a fourth step of forming a copper foil layer by electroplating process on one surface of the metal plating layer; The inorganic filler may include spherical silica having an average particle diameter of 50 to 250 nm.

As a preferred embodiment of the present invention, the inorganic filler of the method for producing a flexible copper foil laminated film of the present invention may satisfy all of the following conditions (1) and (2).

≤ 4.34(1) 2.88 ≤

≤ 4.34

(2) 19.4 nm ≤ D10 ≤ 29.3 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, 444.8 nm ≤ D90 ≤ 667.2 nm

In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.

As a preferred embodiment of the present invention, the first step of the method for producing a flexible copper foil laminated film of the present invention is a compound represented by the following formula (1), a compound represented by the formula (2), a compound represented by the following formula (4), Step 1-1 to prepare a first polymer by mixing and polymerizing the compound represented by the formula (6), the compound represented by the formula (7) and the solvent, the compound represented by the formula (1) to the first polymer, to the formula (5) Step 1-2 to prepare a second polymer by mixing and polymerizing the compound, the compound represented by the following formula and a solvent and the inorganic filler, a catalyst and a solvent to the second polymer to prepare a polyamic acid solution It may include steps 1-3.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 5, R ₁ and R ₂ are each independently -H or an alkyl group of C1 to C5,

[Formula 6]

In Formula 6, R ₃ and R ₄ are each independently, an alkylene group of C1 ~ C7, R ₅ , R ₆ , R ₇ and R ₈ are each independently -H or an alkyl group of C1 ~ C5,

[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently -H or C1 ~ It is an alkyl group of C5, n is a free number which is 1-20.

As a preferred embodiment of the present invention, the polyamic acid solution of the method for producing a flexible copper foil laminated film of the present invention may include 0.67 to 1.02 parts by weight of inorganic filler and 0.27 to 0.41 parts by weight of catalyst based on 100 parts by weight of the second polymer. have.

As a preferred embodiment of the present invention, the second step of the method for producing a flexible copper foil laminated film of the present invention after applying a polyamic acid solution on one side or both sides of a polyimide substrate, and then dried for 1 to 5 minutes at 120 ~ 220 ℃ After the heat treatment, the polyimide substrate layer may be prepared by heat treatment at 280 to 320 ° C. for 1 to 5 minutes.

In a preferred embodiment of the present invention, the third step of the method for producing a flexible copper foil laminated film of the present invention is a first comprising a nickel or nickel-copper alloy in the sputtering process on one or both sides of the polyimide substrate layer Step 3-1 to form a metal plating layer, it may include a step 3-2 to form a second metal plating layer containing copper in the sputtering process on one surface of the first metal plating layer.

As a preferred embodiment of the present invention, the sputtering process of step 3-1 of the method for manufacturing a flexible copper foil laminated film of the present invention is 20 ~ 20 inert gas in a vacuum chamber (champer) is placed nickel or nickel-copper alloy By injection at 80 cc / min, it can proceed at a film formation rate of 20 to 40 nm / min under 1 x 10 ^-2 to 1 x 10 ^-5 Torr pressure.

As a preferred embodiment of the present invention, the sputtering process of step 3-2 of the method for manufacturing a flexible copper foil laminated film of the present invention by injecting an inert gas into the vacuum chamber (champer) is placed 80 ~ 120cc / min At 1 x 10 ^-2 to 1 x 10 ^-5 Torr pressure, it can proceed at 50 to 400 nm / min deposition rate.

As a preferred embodiment of the present invention, the electrolytic plating process of the fourth step of the method for producing a flexible copper foil laminated film of the present invention is a copper current density of 1 ~ 3A / dm 2, under a temperature condition of 25 ~ 40 ℃, copper It may proceed in a mixed solution containing a precursor.

Furthermore, the flexible printed circuit board of the present invention includes the aforementioned flexible copper foil laminated film.

The flexible copper foil laminated film of the present invention and its manufacturing method not only have a thin thickness, but also have remarkably excellent peel strength, tensile strength, elastic modulus, elongation, moisture absorption rate and heat resistance.

1 is a view schematically showing a cross-section of a flexible copper foil laminated film according to an embodiment of the present invention.
2 is a view schematically showing a cross section of a flexible copper foil laminated film according to another preferred embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

1 and 2, in the flexible copper clad layer of the present invention, a polyimide base layer 10, a metal plating layer 20, and a copper foil layer 30 are sequentially stacked. .

First, the polyimide base layer 10 may include a polyimide resin as an electrical insulation layer, and such a polyimide resin is an insoluble, insoluble, ultra high temperature resistant resin that is thermally oxidized, heat resistant, radiation resistant, low temperature, It may have excellent properties such as chemical resistance.

Specifically, the polyimide base layer 10 may include a first polyimide base layer 11 and a second polyimide base layer 12 formed on one side or both sides of the first polyimide base layer 11. In other words, as shown in FIG. 1, the second polyimide base layer 12 may be formed only on one surface of the first polyimide base layer 11, and as shown in FIG. 2, the second polyimide base layer 12 ′. , 12 ") may be formed on both surfaces of the first polyimide substrate layer 11.

The first polyimide base layer 11 of the present invention is a solution of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative. It may include, and preferably comprises an imidization reaction of a compound represented by the following formula (4), a compound represented by the formula (8), a compound represented by the formula (9) and a polyamic acid polymerized by the compound represented by the formula (10) can do.

[Formula 4]

[Formula 8]

[Formula 9]

[Formula 10]

The thickness of the first polyimide base layer 11 is not particularly limited, but may be 5 μm to 25 μm, preferably 12.5 μm to 25 μm in consideration of the thickness of the flexible copper foil laminated film to be manufactured.

The second polyimide substrate layer 12, 12 ', 12 "of the present invention is a compound represented by the following formula (1), a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4) , A compound represented by the following Chemical Formula 5, a compound represented by the following Chemical Formula 6, and an imidation reaction product of a polyamic acid polymerized with the compound represented by the following Chemical Formula 7.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 5]

In Formula 5, R ₁ and R ₂ may be each independently a -H or an alkyl group of C1 ~ C5, preferably a C1 ~ C3 alkyl group.

[Formula 6]

In Formula 6, R ₃ and R ₄ may each independently be an alkylene group of C1 to C7, preferably each independently may be an alkylene group of C2 to C5.

In addition, in Chemical Formula 6, R ₅ , R ₆ , R ₇ and R ₈ may be each independently -H or an alkyl group of C1 ~ C5, preferably each independently may be an alkyl group of C1 ~ C3.

[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, preferably, each independently, may be an alkylene group of C2 ~ C5.

In addition, in Chemical Formula 7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _15, and R ₁₆ may be each independently -H or an alkyl group of C1 to C5, preferably each independently C1 to C3 It may be an alkyl group of.

In addition, in Chemical Formula 7, n may be a rational number of 1 to 20, preferably 4 to 16 rational number, and more preferably 6 to 10 rational number.

On the other hand, the polyamic acid of the present invention is a compound represented by formula 1, a compound represented by formula 2, a compound represented by formula 3, a compound represented by formula 4, a compound represented by formula 5, a compound represented by formula 6 and It may be a polymer obtained by polymerizing a compound represented by Formula 7.

At this time, the polyamic acid of the present invention is 94.9 to 142.5 parts by weight, preferably 106.8 to 130.6 parts by weight, more preferably 112.7 to 124.7 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 It may be polymerized to include a part, if the compound represented by the formula (2) is less than 94.9 parts by weight may have a problem of adhesion and processability deterioration, if it exceeds 142.5 parts by weight may have a problem of dimensional stability and heat resistance.

In addition, the polyamic acid of the present invention is 30.0 to 38.0 parts by weight, preferably 31.0 to 37.5 parts by weight, more preferably 32.0 to 36.8 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 If the compound represented by Formula 3 is less than 27.5 parts by weight, there may be problems of dimensional stability and heat resistance, and if it exceeds 41.3 parts by weight, there may be a problem of deterioration in adhesion and processability.

In addition, the polyamic acid of the present invention is 6.8 to 10.3 parts by weight, preferably 7.6 to 9.4 parts by weight, more preferably 8.1 to 9.0 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 If the compound represented by Formula 4 is less than 6.8 parts by weight, there may be problems of dimensional stability and heat resistance, and if it exceeds 10.3 parts by weight, there may be a problem of deterioration of adhesion and processability.

In addition, the polyamic acid of the present invention is 17.2 to 26.0 parts by weight, preferably 19.4 to 23.8 parts by weight, more preferably 20.5 to 22.7 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 It may be polymerized to include, if the compound represented by the formula (5) is less than 17.2 parts by weight may have a problem of lowering the heat resistance, if it exceeds 26.0 parts by weight may have a problem of lowering the adhesion.

In addition, the polyamic acid of the present invention is 8.3 to 12.6 parts by weight, preferably 9.4 to 11.5 parts by weight, more preferably 9.9 to 11.0 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 It may be polymerized to include, if the compound represented by the formula (6) is less than 8.3 parts by weight may have a problem of adhesion, if it exceeds 12.6 parts by weight may have a problem of heat resistance.

In addition, the polyamic acid of the present invention is 7.1 to 10.8 parts by weight of the compound represented by the formula (7), preferably 8.0 to 9.9 parts by weight, more preferably 8.4 to 9.4 parts by weight based on 100 parts by weight of the compound represented by the formula (1) It may be polymerized, including, if the compound represented by the formula (7) is less than 7.1 parts by weight may have a problem of coating properties and adhesion deterioration, if it exceeds 10.8 parts by weight may be a problem of heat resistance.

Meanwhile, the compound represented by Chemical Formula 6 and the compound represented by Chemical Formula 7 may be included in a weight ratio of 1: 0.68 to 1.03, preferably 1: 0.76 to 0.95, and more preferably 1: 0.81 to 0.90 by weight. , If the compound represented by the formula (7) to less than 0.68 weight ratio with respect to the compound 1 weight ratio represented by the formula (6) may have a problem of lowering the adhesion, if it contains more than 1.03 weight ratio may have a problem of lowering the heat resistance .

The thickness of the second polyimide base layer 12, 12 ', 12 "is not particularly limited, but considering the thickness of the flexible copper foil laminated film to be manufactured 0.5㎛ ~ 5㎛, preferably 1㎛ ~ 3㎛ If the thickness of the second polyimide base layer 12, 12 ', 12 "exceeds 5 [mu] m, the cost increases due to the fact that the adhesive strength due to the thickness increase does not increase proportionally. However, due to the difference in the coefficient of linear expansion between the second polyimide base layer 12, 12 ', 12 "and the first polyimide base layer 11, wrinkles, curls, etc. may occur, which may result in an appearance that is not good. In addition, when the thickness of the second polyimide base layer 12, 12 ', 12 "is less than 0.5 mu m, the second polyimide base layer 12, 12', 12" and the first polyimide base layer 11 Adhesion between the two may be reduced.

Furthermore, the polyimide substrate layer 10 of the present invention is the first polyimide substrate layer 11 and the second polyimide substrate layer 12 is 1: 0.12 ~ 0.19 thickness ratio, preferably 1: 0.14 ~ 0.18 thickness ratio, More preferably, it may have a thickness ratio of 1: 0.15 to 0.17.

Meanwhile, the polyimide base layer 10 of the present invention may include an inorganic filler, and specifically, the inorganic filler may include a first polyimide base layer constituting the polyimide base layer 10. It can contain in both (11) and the 2nd polyimide base material layer 12.

However, the first polyimide base layer 11 may include amorphous calcium phosphate (Ca ₃ (PO ₄ ) ₂ ) as the inorganic filler, and the average particle diameter of the amorphous calcium phosphate is 1 to 7 μm, preferably 1 to 5 μm, more preferably 1 to 3 μm, and if the average particle diameter of amorphous calcium phosphate is less than 1 μm, there may be a problem that wrinkles occur during winding or conveyance in the film manufacturing process, and 7 μm If exceeded, there may be a problem in that the mechanical properties of the film are degraded due to physical damage to the film.

In addition, the first polyimide base layer 11 may contain 1% by weight or less of calcium phosphate, preferably 0.1 to 0.8% by weight, and if it contains more than 1% by weight of calcium phosphate, There may be a problem that the light transmittance is reduced and the mechanical properties of the film are greatly impaired.

In addition, the second polyimide base layer 12 may include spherical silica (SiO ₂ ) as an inorganic filler, and the average particle diameter of the spherical silica is 50 to 250 nm, preferably 70 to 230 nm, more preferably 100 to If the average particle diameter of the silica is less than 50nm, there may be a problem that does not provide the proper running performance of the film or increase the unnecessary amount, if it exceeds 250nm, after fabricating the flexible circuit board, fine pattern due to the appearance protrusion There may be a problem of difficulty in formation.

In addition, the second polyimide substrate layer 12 may include 0.5 to 5% by weight of silica, preferably 1 to 3% by weight of the total weight, and if the silica is included in less than 0.5% by weight of the film There may be a problem that does not provide the proper runability, if included in excess of 5% by weight may have a problem of reduced adhesion, as well as a decrease in light transmittance and a significant damage to the mechanical properties of the film.

In addition, the silica of the second polyimide base layer 12 may satisfy both of the following conditions (1) and (2).

≤ 4.34, 바람직하게는 3.25 ≤

≤ 3.98, 더욱 바람직하게는 3.43 ≤

≤ 3.79(1) 2.88 ≤

≤ 4.34, preferably 3.25 ≤

≤ 3.98, more preferably 3.43 ≤

≤ 3.79

가 2.88 미만이면 필름의 주행성 저하 및 주름 불량 발생의 문제가 있을 수 있고, 4.34를 초과하면 입자의 크기가 크고 입자들의 뭉침으로 인하여 돌기형성으로 인한 외관불량의 문제가 있을 수 있다.If, under condition (1)

If less than 2.88 there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, if it exceeds 4.34 there may be a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles.

(2) 19.4 nm ≤ D10 ≤ 29.3 nm, preferably 21.9 nm ≤ D10 ≤ 26.8 nm, more preferably 23.1 nm ≤ D10 ≤ 25.6 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, preferably 132.4 nm ≤ D50 ≤ 162.0 nm, more preferably 139.8 nm ≤ D50 ≤ 154.6 nm, 444.8 nm ≤ D90 ≤ 667.2 nm, preferably 500.4 nm ≤ D90 ≤ 611.6 nm, more preferably 528.2 nm ≤ D90 ≤ 583.8 nm

If, in condition (2), D10 is less than 23.1 nm, there may be a problem of deterioration of runability of the film and occurrence of wrinkles. If it exceeds 25.6 nm, the particle size is large and the appearance defects due to protrusion formation due to aggregation of the particles may occur. There may be a problem. In addition, if the D50 is less than 117.7nm, there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, and if the D50 exceeds 176,7nm may have a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles. have. In addition, if D90 is less than 444.8nm, there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, and if it exceeds 667.2nm, there may be a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles. .

In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.

Next, the metal plating layer 20 of the present invention may be formed on one surface or both surfaces of the polyimide substrate layer 10. In this case, the metal plating layer 20 may be formed through a sputtering process.

In addition, the metal plating layer 20 of the present invention includes a first metal plating layer 21 formed on one surface of the second polyimide base layer 12 and a second metal plating layer 22 formed on one surface of the first metal plating layer 21. can do.

In other words, as shown in FIG. 1, the second polyimide base layer 12 is formed on only one surface of the first polyimide base layer 11, or as shown in FIG. 2, the second polyimide base layer 12 ′ and 12. When ") is formed on both sides of the first polyimide substrate layer 11, the first metal plating layers 21, 21 ', 21 " are formed on one surface of the second polyimide substrate 12, 12', 12 " The second metal plating layers 22, 22 ', and 22 "may be formed on one surface of the first metal plating layers 21, 21' and 21". In this case, the first metal plating layer 21 and the second metal plating layer may be formed. Reference numeral 22 may be formed through a sputtering process.

The first metal plating layers 21, 21 ', 21 "of the present invention may include nickel or a nickel-copper alloy, and the thickness of the first metal plating layers 21, 21', 21" is not particularly limited. Considering the thickness of the flexible copper foil laminated film to be produced may be 10 to 40nm, preferably 15 to 35nm, more preferably 20 to 30nm.

The second metal plating layers 22, 22 'and 22 "of the present invention may include copper, and the thickness of the second metal plating layers 22, 22' and 22" is not particularly limited, but the flexible copper foil to be manufactured Considering the thickness of the laminated film may be 50 ~ 300nm, preferably 100 ~ 150nm.

Meanwhile, in the metal plating layer 20 of the present invention, the first metal plating layer 21 and the second metal plating layer 22 have a thickness ratio of 1: 4.8 to 7.2, preferably 1: 5.4 to 6.6 thickness ratio, and more preferably 1: 1. It may have a thickness ratio of 5.7 to 6.3, and if the second metal plating layer 22 is less than the thickness ratio of 4.8 with respect to the thickness ratio of the first metal plating layer 21, the resistance may be increased, so that electroplating may be impossible. If exceeded, thermal shock may be applied to the surface of the polyimide substrate layer 10, thereby increasing the pinholes.

Finally, the copper foil layer 30 of the present invention may be formed on one surface of the metal plating layer 20.

In other words, as shown in FIG. 1, the second polyimide base layer 12 is formed on only one surface of the first polyimide base layer 11, or as shown in FIG. 2, the second polyimide base layer 12 ′ and 12. When ") is formed on both sides of the first polyimide substrate layer 11, the first metal plating layers 21, 21 ', 21 " are formed on one surface of the second polyimide substrate 12, 12', 12 " , The second metal plating layers 22, 22 ′ and 22 ″ are formed on one surface of the first metal plating layers 21, 21 ′ and 21 ″, and the copper foil layers 30, 30 ′ and 30 ″ are formed on the second metal plating layer ( 22, 22 ', 22 ") may be formed on one surface.

In addition, the copper foil layer 30 of the present invention exhibits conductivity and ductility, and may be provided with a circuit pattern, and the circuit pattern may be formed by patterning the desired shape according to a design purpose.

In addition, the copper foil layer 30 of the present invention may be formed through an electroplating process.

The thickness of the copper foil layer 30 is not particularly limited, but may be 1 to 20 μm, preferably 2 to 15 μm, and more preferably 5 to 13 μm in consideration of the thickness of the flexible copper foil laminated film to be manufactured.

Furthermore, the flexible copper foil laminated film of the present invention may have a peel strength of 1,000 to 1,400 gf / cm, preferably 1,100 to 1,300 gf / cm, when measured according to the PC-TM-650 2.4.9 standard. have.

In addition, the flexible copper foil laminated film of the present invention may have heat resistance of 300 to 340 ° C., preferably 305 to 320 ° C., as measured according to JIS C6471 standard.

In addition, the flexible copper foil laminated film of the present invention, when measured according to the IPC-TM-650 2.4.19 standard, tensile strength of 176 ~ 264 MPa, preferably 198 ~ 242 MPa, more preferably 210 ~ It can have a tensile strength of 230 MPa.

In addition, the flexible copper foil laminated film of the present invention, when measured according to the IPC-TM-650 2.4.18.3 standard, the elastic modulus of 4.64 ~ 6.95 GPa, preferably the elastic modulus of 5.22 ~ 6.38 GPa, more preferably 5.5 ~ 6.1 GPa It can have an elastic modulus of.

In addition, the flexible copper foil laminated film of the present invention, when measured according to the IPC-TM-650 2.4.19 standard, elongation of 28 to 42%, preferably elongation of 31.5 to 38.5%, more preferably 33.5 to 36.5% It may have an elongation of.

In addition, the flexible copper foil laminated film of the present invention, when measured according to the IPC-TM-650 2.6.2 standard, the moisture absorption of 1.52 ~ 2.28%, preferably the moisture absorption of 1.71 ~ 2.09%, more preferably 1.8 ~ It may have a moisture absorption rate of 2.0%.

On the other hand, the present invention provides a flexible printed circuit board comprising the aforementioned flexible copper foil laminated film.

Flexible printed circuit boards (FPCB) is an electronic component developed as the electronic products become smaller and lighter, the flexible printed circuit board including the flexible copper foil laminated film of the present invention has excellent physical properties.

The flexible printed circuit board of the present invention is a core component of electronic products such as mobile phones, cameras, laptops, wearable devices, computers and peripherals, mobile communication terminals, video and audio devices, camcorders, printers, DVD players, TFT LCD displays, satellites It may be used in at least one of the equipment, military equipment, medical equipment, preferably in at least one of a mobile phone, a camera, a notebook and a wearable device.

On the other hand, the method for producing a flexible copper foil laminated film of the present invention includes the first step to the fourth step.

First, the first step of the method for producing a flexible copper foil laminated film may be a polyamic acid solution.

The polyamic acid solution may be prepared through the following first-first to third steps.

Step 1-1 is a mixture of a compound represented by the following formula (1), a compound represented by the formula (2), a compound represented by the formula (4), a compound represented by the formula (6), a compound represented by the formula (7) and a solvent and The first polymer may be prepared by polymerization.

[Formula 1]

[Formula 2]

[Formula 4]

[Formula 6]

In Formula 6, R ₃ and R ₄ may each independently be an alkylene group of C1 to C7, preferably each independently may be an alkylene group of C2 to C5.

In addition, in Chemical Formula 6, R ₅ , R ₆ , R ₇ and R ₈ may be each independently -H or an alkyl group of C1 ~ C5, preferably each independently may be an alkyl group of C1 ~ C3.

[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, preferably, each independently, may be an alkylene group of C2 ~ C5.

In addition, in Chemical Formula 7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _15, and R ₁₆ may be each independently -H or an alkyl group of C1 to C5, preferably each independently C1 to C3 It may be an alkyl group of.

In addition, in Chemical Formula 7, n may be a rational number of 1 to 20, preferably 4 to 16 rational number, and more preferably 6 to 10 rational number.

The solvent of step 1-1 includes at least one of N-Methyl Pyrrolidone (NMP), Dimethylformamide (DMF), N, N-Dimethylacetamide (DMAc), N-Methyl Pyrrolidone (NMP), and γ-Butyrolactone (GBL). It may include one or more of, and may preferably include one or more of N-Methyl Pyrrolidone (NMP) and dimethylformamide (DMF).

Specifically describing step 1-1, first, the compound represented by the formula (1), the compound represented by the formula (4), the compound represented by the formula (6) and the compound and the solvent represented by the formula (7) are 5 ~ 30 ℃, preferably Preferably 10 to 20 ℃, 15 to 60 minutes, preferably 20 to 45 minutes to mix first, the compound represented by the formula (BTDA) 1 to 5 times, preferably divided into 2 to 4 times, The first polymer may be prepared by mixing and polymerizing for 10 to 20 ° C., preferably for 12 to 18 ° C., for 30 to 90 minutes, preferably for 45 to 75 minutes.

In addition, the first polymer is 10.3 to 15.5 parts by weight of the compound represented by Formula 4, preferably 11.6 to 14.2 parts by weight, and 12.6 to 19.0 parts by weight of the compound represented by Formula 6, based on 100 parts by weight of the compound represented by Formula 1 , Preferably 14.2 to 17.4 parts by weight and 10.8 to 16.3 parts by weight of the compound represented by the formula (7), preferably 12.1 to 14.9 parts by weight of the polymer.

In addition, the solvent used to prepare the first polymer may include 1264 to 1897 parts by weight of solvent, preferably 1422 to 1739 parts by weight, based on 100 parts by weight of the compound represented by Formula 1.

Step 1-2 is a second polymer by mixing and polymerizing a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 5, a compound represented by Chemical Formula 3, and a solvent with the first polymer prepared in Step 1-1 Polymers can be prepared.

[Formula 3]

[Formula 5]

In Formula 5, R ₁ and R ₂ may be each independently a -H or an alkyl group of C1 ~ C5, preferably a C1 ~ C3 alkyl group.

The solvent of step 1-2 is at least one of DMSO (Dimethyl Sulfoxide), DMF (N, N-Dimethylformamide), DMAc (N, N-Dimethylacetamide), NMP (N-Methyl Pyrrolidone) and GBL (γ-Butyrolactone) It may include, and may preferably include one or more of N-Methyl Pyrrolidone (NMP) and dimethylformamide (DMF).

Specifically, steps 1-2 will be described in detail. In the first polymer prepared in Step 1-1, the compound represented by Formula 1, the compound represented by Formula 5, and the solvent are 0 to 30 ° C., preferably 10 to 20 ° C. At 10 to 60 minutes, preferably 20 to 40 minutes, and then the compound represented by the formula (3) is added, 10 to 20 ℃, preferably 12 to 18 ℃, 30 to 180 minutes, preferably The second polymer can be prepared by mixing and polymerizing for 40-120 minutes.

Further, the second polymer is 81.3 to 122.0 parts by weight of the compound represented by Formula 3, preferably 91.4 to 111.8 parts by weight, and 51.0 to 76.6 parts by weight of the compound represented by Formula 5, based on 100 parts by weight of the compound represented by Formula 1 Preferably, the polymer may be polymerized from 57.4 to 70.3 parts by weight.

In addition, the solvent used to prepare the second polymer may include 1040 to 1561 parts by weight of solvent, preferably 1170 to 1431 parts by weight, based on 100 parts by weight of the compound represented by Formula 1.

In the step 1-3, a polyamic acid solution may be prepared by mixing an inorganic filler, a catalyst, and a solvent with the second polymer prepared in the step 1-2.

The inorganic filler of the first to third stages may include at least one of silica, aluminum hydroxide and calcium carbonate in magnesium hydroxide, preferably silica, and more preferably spherical Silica (SiO ₂ ) may be included, and the average particle diameter of the spherical silica may be 50 to 250 nm, preferably 70 to 230 nm, more preferably 100 to 200 nm, and if the average particle diameter of the silica is less than 50 nm, There may be a problem of failing to impart proper runability or increase an unnecessary amount, and if it exceeds 250 nm, there may be a problem of difficulty in forming a fine pattern due to appearance protrusions after fabricating the flexible circuit board.

 In addition, silica can satisfy | fill both the following conditions (1) and conditions (2).

≤ 4.34, 바람직하게는 3.25 ≤

≤ 3.98, 더욱 바람직하게는 3.43 ≤

≤ 3.79(1) 2.88 ≤

≤ 4.34, preferably 3.25 ≤

≤ 3.98, more preferably 3.43 ≤

≤ 3.79

가 2.88 미만이면 필름의 주행성 저하 및 주름 불량 발생의 문제가 있을 수 있고, 4.34를 초과하면 입자의 크기가 크고 입자들의 뭉침으로 인하여 돌기형성으로 인한 외관불량의 문제가 있을 수 있다. If, under condition (1)

If less than 2.88 there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, if it exceeds 4.34 there may be a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles.

(2) 19.4 nm ≤ D10 ≤ 29.3 nm, preferably 21.9 nm ≤ D10 ≤ 26.8 nm, more preferably 23.1 nm ≤ D10 ≤ 25.6 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, preferably 132.4 nm ≤ D50 ≤ 162.0 nm, more preferably 139.8 nm ≤ D50 ≤ 154.6 nm, 444.8 nm ≤ D90 ≤ 667.2 nm, preferably 500.4 nm ≤ D90 ≤ 611.6 nm, more preferably 528.2 nm ≤ D90 ≤ 583.8 nm

If the D10 is less than 23.1 nm under the condition (2), there may be a problem of deterioration of the running property of the film and occurrence of wrinkles. If the thickness exceeds 25.6 nm, the size of the particles is large and the appearance due to the formation of protrusions due to the aggregation of the particles. There may be a problem of badness. In addition, if the D50 is less than 117.7nm, there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, and if the D50 exceeds 176,7nm may have a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles. have. In addition, if D90 is less than 444.8nm, there may be a problem of deterioration of the runability of the film and the occurrence of wrinkle defects, and if it exceeds 667.2nm, there may be a problem of appearance defects due to protrusions due to the large size of the particles and agglomeration of the particles. .

In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.

In addition, the catalyst of steps 1-3 may include at least one of isoquinoline, β-picoline, pyridine, dimethylaniline, and trimethylamine. It may preferably include isoquinoline (Isoquinoline).

In addition, the solvent of steps 1-3 is one of DMSO (Dimethyl Sulfoxide), DMF (N, N-Dimethylformamide), DMAc (N, N-Dimethylacetamide), NMP (N-Methyl Pyrrolidone) and GBL (γ-Butyrolactone) It may include more than one species, preferably may include one or more of NMP (N-Methyl Pyrrolidone) and DMF (Dimethylformamide).

Meanwhile, the polyamic acid solution of step 3-1 may include 0.67 to 1.02 parts by weight of inorganic filler, preferably 0.76 to 0.94 parts by weight, based on 100 parts by weight of the second polymer. If the inorganic filler contains less than 0.67 parts by weight, there may be a problem in that it does not provide proper runability to the film. If it contains more than 1.02 parts by weight, the light transmittance and the mechanical properties of the film may be deteriorated. There may be.

In addition, the polyamic acid solution of step 3-1 may include 0.27 to 0.41 parts by weight, preferably 0.3 to 0.38 parts by weight, based on 100 parts by weight of the second polymer.

In addition, the polyamic acid solution of step 3-1 may include 55.3 ~ 83.1 parts by weight of solvent, preferably 62.3 ~ 76.2 parts by weight based on 100 parts by weight of the second polymer.

Next, in the second step of the method for producing a flexible copper foil laminated film, a polyimide base layer may be prepared by applying the polyamic acid solution prepared in the first step to one or both sides of the polyimide base.

Specifically, the second step is after applying the polyamic acid solution to one or both sides of the polyimide substrate, and then dried for 1 to 5 minutes, preferably 2 to 4 minutes at 120 ~ 220 ℃, preferably 150 ~ 190 ℃ , 280 ~ 320 ℃, preferably 290 ~ 310 ℃ heat treatment for 1 to 5 minutes, preferably 2 to 4 minutes to prepare a polyimide substrate layer. More specifically, the polyamic acid solution is imidized by imidization through heat treatment at 280 to 320 ° C., preferably at 290 to 310 ° C., for 1 to 5 minutes, and preferably for 2 to 4 minutes. The polyimide substrate may be prepared by forming an imidization reaction product of polyamic acid on one or both sides of the polyimide substrate.

Next, the third step of the method for producing a flexible copper foil laminated film may form a metal plating layer by sputtering on one or both sides of the polyimide substrate layer prepared in the second step.

The metal plating layer may be formed through steps 3-1 and 3-2.

First, step 3-1 may form a first metal plating layer including nickel or a nickel-copper alloy by sputtering on one or both sides of the polyimide substrate layer. At this time, in the sputtering process of the step 3-1, an inert gas is injected at 20 to 80 cc / min, preferably 40 to 60 cc / min into a vacuum chamber in which nickel or a nickel-copper alloy is disposed, and thus 1 x It can proceed at a deposition rate of 20 to 40 nm / min, preferably 25 to 35 nm / min under a pressure of 10 ^-2 to 1 x 10 ^-5 Torr, preferably 1 x 10 ^-3 to 1 x 10 ^-4 Torr. have. In addition, at least one of argon (Ar) and nitrogen (N 2) may be used as the inert gas of step 3-1, and argon (Ar) may be preferably used.

Next, in step 3-2, a second metal plating layer including copper may be formed on one surface of the first metal plating layer by a sputtering process. At this time, the sputtering process of the step 3-2 is injected inert gas at 50 ~ 150cc / min, preferably 70 ~ 120 cc / min in a vacuum chamber (cuper) is placed copper, 1 x 10 ^-2 ~ It can proceed at a traveling speed of 50 to 400 nm / min, preferably 80 to 150 nm / min under 1 x 10 ^-5 Torr, preferably 1 x 10 ^-3 to 1 x 10 ^-4 Torr. In addition, at least one of argon (Ar) and nitrogen (N 2) may be used as the inert gas of steps 3-1 and 3-2, and argon (Ar) may be preferably used.

Finally, in the fourth step of the method for manufacturing a flexible copper foil laminated film, the copper foil layer may be formed by electroplating on one surface of the metal plating layer formed in the third step. In other words, the copper foil layer may be formed on one surface of the second metal plating layer formed in step 3-2 by an electroplating process.

Specifically, the electrolytic plating process of the fourth step is a cathode current density of 1 ~ 3A / dm 2, preferably a cathode current density of 1.5 ~ 2.5A / dm 2, temperature conditions of 25 ~ 40 ℃, preferably 28 ~ Under the temperature condition of 36 degreeC, it can advance in the mixed solution containing a copper precursor, and can form a copper foil layer.

The mixed solution is not particularly limited as a copper precursor, but copper sulfate hydrate (CuSO ₄ H20) or the like may be used. In addition, the mixed solution may include sulfuric acid, chlorine, thiourea and dextrin in addition to the copper precursor.

The present invention has been described above with reference to the embodiment, which is merely an example and is not intended to limit the embodiment of the present invention. Those skilled in the art to which the embodiments of the present invention belong will have the essential characteristics of the present invention. It will be appreciated that various modifications and applications not illustrated above are possible without departing from the scope of the invention. For example, each component specifically shown in the embodiment of the present invention may be modified. And differences relating to such modifications and applications will be construed as being included in the scope of the invention defined in the appended claims.

Example 1 Preparation of Flexible Copper Foil Laminated Film

(1) 4.81 g of the compound represented by the following Chemical Formula 1-1, 0.76 g of the compound represented by the following Chemical Formula 6-1, 0.65 g of the compound represented by the following Chemical Formula 7-1, 0.62 g of the compound represented by the following Chemical Formula 4, NMP 53 g of (N-Methyl Pyrrolidone) and 23 g of DMF (dimethylformamide) were first mixed at 15 ° C. for 30 minutes, and 8.63 g of the compound represented by the following Formula 2 was added three times, and mixed and polymerized at 15 ° C. for 1 hour to prepare a mixture. One polymer was prepared.

(2) 2.46 g of the compound represented by the following Chemical Formula 1-1, 1.57 g of the compound represented by the following Chemical Formula 5-1, 22 g of N-Methyl Pyrrolidone (NMP), and 10 g of DMF (Dimethylformamide) were added to the first polymer at 15 ° C. First, the mixture was mixed for 1 minute, and 8.63 g of the compound represented by the following Chemical Formula 3 was added thereto, followed by mixing and polymerizing at 15 ° C. for 60 minutes to prepare a second polymer.

(3) 1.10 g of a 40% by weight solution of spherical silica (average diameter) having an average particle diameter of 100 nm as an inorganic filler in 130 g of a second polymer, 0.44 g of isoquinoline as a catalyst, 63 g of N-Methyl Pyrrolidone (NMP), A polyamic acid solution was prepared by mixing 27 g of dimethylformamide (DMF).

(4) Amorphous as an imide reactant and inorganic filler of a polyamic acid polymerized by a compound represented by the following formula (4), a compound represented by the following formula (8), a compound represented by the following formula (9), and a compound represented by the following formula (10-1) Evenly apply the polyamic acid solution prepared on both sides of the polyimide substrate (thickness: 19 ㎛) (SKC KOLON PI, GTO75) containing calcium phosphate, and in-line drying oven for 3 minutes at 170 ℃ ), And then heat-treated in an in-line drying oven at 300 ° C. for 3 minutes to prepare a polyimide substrate layer. At this time, the polyamic acid solution was imidized to form a layer having a thickness of 3 μm on both sides of the polyimide substrate.

In addition, the layer formed by the polyamic acid solution contained 2% by weight of spherical silica in the total weight.

(5) A first metal plating layer (= nickel-copper alloy layer) having a thickness of 25 nm was formed on both sides of the polyimide substrate layer by a sputtering process. At this time, the sputtering process injects 50 cc / min of argon (Ar) gas into a vacuum chamber in which 30 wt% of nickel-copper alloy is placed, and at a film formation rate of 30 nm / min under 1 x 10 ^-3 Torr pressure. Proceeded.

(6) A second metal plating layer (= copper layer) having a thickness of 150 nm was formed on one surface of the first metal plating layer by a sputtering process. At this time, in the sputtering process, 100 cc / min of argon (Ar) gas was injected into a vacuum chamber in which copper was disposed, and then progressed at a film formation rate of 100 nm / min under 1 x 10 ^-3 Torr pressure.

(7) A flexible copper foil laminated film was prepared by forming a copper foil layer having a thickness of 10 μm on one surface of the second metal plating layer by an electroplating process. At this time, the electrolytic plating process was carried out in a mixed solution containing copper sulfate hydrate (CuSO ₄ H20), sulfuric acid, chlorine, thiourea and dextrin under a cathode current density of 2 A / dm 2, and a temperature of 32 ° C. It became.

[Formula 1-1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5-1]

In Formula 5-1, R ₁ and R ₂ are methyl groups.

[Formula 6-1]

In Formula 6-1, R ₃ and R ₄ are —CH ₂ CH ₂ CH ₂ —, and R ₅ , R ₆ , R ₇ and R ₈ are methyl groups.

[Formula 7-1]

In Formula 7-1, R ₉ and R ₁₀ are —CH ₂ CH ₂ CH ₂ —, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _15, and R ₁₆ are methyl groups, and n is a rational number 8. to be.

[Formula 8]

[Formula 9]

[Formula 10-1]

Example 2

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, to prepare a polyamic acid solution, silica having an average particle diameter of 200 nm was used instead of silica having an average particle diameter of 100 nm.

Example 3

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, 0.55 g of a 40 wt% spherical silica solution was used to prepare a polyamic acid solution.

The layer formed by the polyamic acid solution contained 1% by weight of spherical silica in the total weight.

Example 4

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, 1.65 g of a 40 wt% spherical silica solution was used to prepare a polyamic acid solution.

The layer formed by the polyamic acid solution contained 3% by weight of spherical silica in the total weight.

Example 5

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, 0.06 g of a 40 wt% spherical silica solution was used to prepare a polyamic acid solution.

The layer formed by the polyamic acid solution contained 0.1% by weight of spherical silica in the total weight.

Example 6

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, 3.85 g of a 40 wt% spherical silica solution was used to prepare a polyamic acid solution.

The layer formed by the polyamic acid solution contained 7% by weight of spherical silica in the total weight.

Comparative Example 1

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, to prepare a polyamic acid solution, silica having an average particle size of 30 nm was used instead of silica having an average particle size of 100 nm.

Comparative Example 2

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, in order to prepare a polyamic acid solution, silica having an average particle diameter of 300 nm was used instead of silica having an average particle diameter of 100 nm.

Comparative Example 3

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, amorphous calcium phosphate was used instead of the constituent silica to prepare a polyamic acid solution.

Comparative Example 4

A flexible copper foil laminated film was prepared in the same manner as in Example 1. However, a flexible copper foil laminated film was manufactured without using the component silica to prepare a polyamic acid solution.

Experimental Example 1

The flexible copper foil laminated films prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated based on the following physical property evaluation method, and the results are shown in Table 1 below.

(1) Peel strength

Peel strength of the flexible copper foil laminated films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were measured according to the IPC-TM-650 standard (IPC-TM-650-method.2.4.9). 10mm in width, peeling angle 90 degrees, peeling speed 50mm / min)

(2) Tensile strength / elongation

In accordance with the IPC-TM-650 standard (IPC-TM-650-method.2.4.19), the tensile strength and elongation of the flexible copper foil laminated films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were measured, respectively. In addition, the measurement was performed about the MD direction of a core film. (Distance between fixtures 100 mm, width 10 mm, tensile speed 100 mm / min)

(3) winding characteristics

When the polyamic acid solution prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was applied to the polyimide substrate, dried and heat treated, the polyamic acid solution was imidized to form a layer on both sides of the polyimide substrate. The state and the presence of wrinkles were confirmed at the time of winding. If wrinkles do not occur and the winding is good, X, some wrinkles are generated, and if the winding is not well done, △, a lot of wrinkles and if not occurred, it is marked as ○.

(4) coating processability

When the polyamic acid solution is applied to the polyimide substrate, dried and heat treated as described in Examples 1 to 9 and Comparative Examples 1 to 3, the polyamic acid solution is imidized to form a layer on both sides of the polyimide substrate, The appearance state was confirmed. In this case, if wrinkles and protrusions do not occur, X, wrinkles and protrusions are partially generated, and if a lot of wrinkles and protrusions are indicated as ○.

As can be seen in Table 1, the flexible copper foil laminated film prepared in Comparative Example 1 is not only poor winding, compared to the flexible copper foil laminated film prepared in Examples 1 to 2, bubbles are generated, the coating processability is inferior I could confirm it.

In addition, compared to the flexible copper foil laminated film prepared in Examples 1 to 2, the flexible copper foil laminated film prepared in Comparative Example 2 was not only inferior in peel strength, tensile strength and elongation, but also in wrinkles, resulting in poor coating processability. Could.

In addition, although the flexible copper foil laminated film prepared in Example 5 may have excellent physical properties, it could be confirmed that it is impossible to use it as a manufactured flexible foil laminated film because wrinkles were generated a lot and winding was impossible.

In addition, compared with Examples 1, 3 to 4, the flexible copper foil laminated film prepared in Example 6 was not only inferior in peel strength, tensile strength and elongation, but also in the presence of a large number of protrusions.

In addition, compared to Example 1, the flexible copper foil laminated film manufactured in Comparative Example 3 was not only inferior in peel strength, tensile strength and elongation, but also in a large amount of protrusions, so that the coating processability was remarkably decreased.

In addition, the flexible copper foil laminated film prepared in Comparative Example 4 may be excellent in physical properties, not only wrinkles are generated a lot of winding and winding is impossible, it can be confirmed that the coating processability is poor due to wrinkles are generated.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (20)

Polyimide base layer;
A metal plating layer formed on one or both surfaces of the polyimide base layer; And
A copper foil layer formed on one surface of the metal plating layer; Including,
The polyimide base layer is a first polyimide base layer; And a second polyimide base layer formed on one or both surfaces of the first polyimide base layer. Including;
The first polyimide base layer contains an amorphous calcium phosphate having an average particle diameter of 1 ~ 7㎛ 1 wt% or less,
The second polyimide substrate layer is a flexible copper foil laminated film, characterized in that it comprises 1 to 3% by weight of spherical silica (silica) having an average particle diameter of 50 to 250nm.
delete The method of claim 1,
The silica of the second polyimide substrate layer satisfies both the following conditions (1) and (2).
(1) 2.88 ≤

≤ 4.34
(2) 19.4 nm ≤ D10 ≤ 29.3 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, 444.8 nm ≤ D90 ≤ 667.2 nm
In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.
The method of claim 1,
The second polyimide substrate layer is a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, a compound represented by Formula 5, A flexible copper foil laminated film further comprising an imidization reaction product of a polyamic acid polymerized with a compound represented by 6 and a compound represented by Formula 7;
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 5, R ₁ and R ₂ are each independently -H or an alkyl group of C1 to C5,
[Formula 6]

In Formula 6, R ₃ and R ₄ are each independently, an alkylene group of C1 ~ C7, R ₅ , R ₆ , R ₇ and R ₈ are each independently -H or an alkyl group of C1 ~ C5,
[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently -H or C1 ~ It is an alkyl group of C5, n is a free number which is 1-20.
The method of claim 4, wherein
The polyamic acid is based on 100 parts by weight of the compound represented by Formula 1, 94.9 to 142.5 parts by weight of the compound represented by Formula 2, 30.0 to 38.0 parts by weight of the compound represented by Formula 3, 6.8 to 10.3 weight by weight of the compound represented by Formula 4 Part, 17.2 to 26.0 parts by weight of the compound represented by the formula (5), 8.3 to 12.6 parts by weight of the compound represented by the formula (6) and 7.1 to 10.8 parts by weight of the compound represented by the formula (7) is a flexible copper foil laminated film characterized in that a polymer.
The method of claim 5,
A flexible copper foil laminated film comprising the compound represented by Formula 6 and the compound represented by Formula 7 in a weight ratio of 1: 0.68 to 1.03.
The method of claim 1,
The polyimide substrate layer is a flexible copper foil laminated film, characterized in that the first polyimide substrate layer and the second polyimide substrate layer has a thickness ratio of 1: 0.12 to 0.19.
The method of claim 1,
The first polyimide substrate layer includes an imidization reaction product of a polyamic acid polymerized with a compound represented by Formula 4, a compound represented by Formula 8, a compound represented by Formula 9, and a compound represented by Formula 10: Flexible copper foil laminated film, characterized in that;
[Formula 4]

[Formula 8]

[Formula 9]

[Formula 10]

The method of claim 1,
The metal plating layer may include a first metal plating layer formed on one surface of the second polyimide base layer; And a second metal plating layer formed on one surface of the first metal plating layer. Including,
The first metal plating layer includes nickel or a nickel-copper alloy,
The second metal plating layer is a flexible copper foil laminated film, characterized in that containing copper.
The method of claim 9,
The metal plating layer is a flexible copper foil laminated film, characterized in that the first metal plating layer and the second metal plating layer has a thickness ratio of 1: 4.8 to 7.2.
A first step of producing a polyamic acid solution containing an inorganic filler;
A second step of preparing a polyimide substrate layer by applying a polyamic acid solution to one or both sides of the polyimide substrate including 1 wt% or less of amorphous calcium phosphate having an average particle diameter of 1 to 7 μm in total weight;
A third step of forming a metal plating layer on one surface or both surfaces of the polyimide substrate layer by a sputtering process; And
A fourth step of forming a copper foil layer on one surface of the metal plating layer by an electroplating process; Including,
The inorganic filler includes spherical silica (silica) having an average particle diameter of 50 ~ 250nm,
The method of manufacturing a flexible copper foil laminate film, characterized in that the layer formed by the polyamic acid solution comprises 1 to 3% by weight of spherical silica (silica) having an average particle diameter of 50 to 250nm in the total weight.
The method of claim 11,
The inorganic filler is a method for producing a flexible copper foil laminated film, characterized in that all of the following conditions (1) and conditions (2) are satisfied.
(1) 2.88 ≤

≤ 4.34
(2) 19.4 nm ≤ D10 ≤ 29.3 nm, 117.7 nm ≤ D50 ≤ 176.7 nm, 444.8 nm ≤ D90 ≤ 667.2 nm
In the above conditions (1) and (2), D10, D50 and D90 refer to particle sizes corresponding to 10%, 50% and 90% with respect to the maximum value in the cumulative distribution of the silica particle sizes, respectively.
The method of claim 11,
The first step is
To the first polymer by mixing and polymerizing a compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (4), a compound represented by the formula (6), a compound represented by the formula (7) and a solvent Manufacturing step 1-1;
Step 1-2 to prepare a second polymer by mixing and polymerizing the compound represented by the following formula (1), the compound represented by the following formula (5), the compound represented by the formula (3) and a solvent to the first polymer; And
Preparing a polyamic acid solution by mixing an inorganic filler, a catalyst, and a solvent with the second polymer;
Method for producing a flexible copper foil laminated film comprising a.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 5, R ₁ and R ₂ are each independently -H or an alkyl group of C1 to C5,
[Formula 6]

In Formula 6, R ₃ and R ₄ are each independently, an alkylene group of C1 ~ C7, R ₅ , R ₆ , R ₇ and R ₈ are each independently -H or an alkyl group of C1 ~ C5,
[Formula 7]

In Formula 7, R ₉ and R ₁₀ are each independently, an alkylene group of C1 ~ C7, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently -H or C1 ~ It is an alkyl group of C5, n is a free number which is 1-20.
The method of claim 13,
The polyamic acid solution is a method for producing a flexible copper foil laminated film, characterized in that it comprises 0.67 ~ 1.02 parts by weight of inorganic filler and 0.27 ~ 0.41 parts by weight of catalyst based on 100 parts by weight of the second polymer.
The method of claim 11,
The second step is to apply a polyamic acid solution to one or both sides of the polyimide substrate, and then dried for 1 to 5 minutes at 120 ~ 220 ℃, heat-treated for 1 to 5 minutes at 280 ~ 320 ℃ to prepare a polyimide substrate layer Method for producing a flexible copper foil laminated film, characterized in that.
The method of claim 11,
The third step is
Forming a first metal plating layer including nickel or a nickel-copper alloy on one or both sides of the polyimide substrate layer by a sputtering process; And
Step 3-2 of forming a second metal plating layer including copper on one surface of the first metal plating layer by a sputtering process;
Method for producing a flexible copper foil laminated film comprising a.
The method of claim 16,
In the sputtering process of step 3-1, 20 to 80 cc / min of inert gas is injected into a vacuum chamber in which nickel or a nickel-copper alloy is disposed, under a pressure of 1 x 10 ^-2 to 1 x 10 ^-5 Torr. Method for producing a flexible copper foil laminated film, characterized in that proceeding at 20 ~ 40 nm / min film forming speed.
The method of claim 16,
In the sputtering process of step 3-2, an inert gas is injected into a vacuum chamber in which copper is disposed, 80 to 120 cc / min, and 50 to 400 nm / under 1 x 10 ^-2 to 1 x 10 ^-5 Torr pressure. min method for producing a flexible copper foil laminated film, characterized in that proceeding at a film forming speed.
The method of claim 11,
The electrolytic plating process of the fourth step is a method for producing a flexible copper foil laminated film, characterized in that the proceeding in a mixed solution containing a copper precursor under a cathode current density of 1 ~ 3A / ㎡, temperature conditions of 25 ~ 40 ℃. .
A flexible printed circuit board comprising the flexible copper foil laminated film according to any one of claims 1 to 10.

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