JP7208352B2 - FLEXIBLE COPPER FILM LAMINATED, ELECTRONIC DEVICE CONTAINING THE SAME, AND METHOD FOR MANUFACTURING SAME FLEXIBLE COPPER FILM LAMINATED FILM - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flexible copper clad laminate film, an electronic device including the same, and a method for producing the flexible copper clad laminate film.

With the accelerated growth of the mobile market and the increasing demand for LCD TV monitors, the development of materials with the characteristics of thin film, small size, light weight, durability and high image quality is required in fields such as electronic products and semiconductor integrated circuits. promoted. In the field of flexible copper clad laminate (FCCL) used in driver integrated circuits (ICs) for LCDs, fine patterning, thinning and durability are also increasingly required.

A flexible copper clad laminate film has a structure in which a circuit pattern is formed on its surface and an electronic device such as a semiconductor chip is mounted on the circuit pattern. Recently, there has been an increase in the number of products in which the pitch of the circuit pattern is 23 μm or less. As the pitch and line width become smaller, instability of dimensional change becomes a problem.

In order to solve such problems, fine circuit pattern forming techniques are also being developed. However, for fine circuit patterning, it is necessary to maintain high adhesive strength between the substrate and the metal layer, and to solve the problem of interlayer delamination of the flexible copper clad laminate film.

Therefore, there is still a need for a flexible copper clad laminate film having excellent dimensional stability between a substrate and a metal layer, an electronic device including the same, and a method for producing the flexible copper clad laminate film.

The problem to be solved by the present invention is to provide a flexible copper foil laminate film with improved crystallinity and dimensional stability.

Another problem to be solved by the present invention is to provide an electronic device including the flexible copper clad laminate film.

Another problem to be solved by the present invention is to provide a method for producing the flexible copper foil laminate film.

According to one aspect,
a non-conductive polymeric substrate;
a nickel-containing plating layer located on at least one surface of the non-conductive polymer substrate;
a copper plating layer located on the nickel-containing plating layer;
A flexible copper clad laminate film is provided in which the copper plating layer has a half-value width fluctuation rate of 0.01° or less in an X-ray diffraction spectrum, which is calculated according to Equation 1 below for the peak of the (111) plane.

The copper plating layer also has a half width of 0.20 to 0.35° for the peak of the (111) plane in the X-ray diffraction spectrum.

Each of the nickel-containing plating layer and the copper plating layer is also an electroless plating layer.

The thickness of said copper layer is also between 40 nm and 150 nm.

After leaving the flexible copper foil laminate film for 1 to 60 days, it is heat-treated at 150° C. for 30 minutes. is also 0.015 or less.

The nickel-containing plating layer may include a nickel layer.

The nickel-containing plating layer also has a thickness of 40 nm to 250 nm.

The non-conductive polymer base material is one or more selected from phenol-based resin, phenol-aldehyde-based resin, allyl-based resin, epoxy-based resin, polyethylene-based resin, polypropylene-based resin, polyester-based resin, and polyimide-based resin. may contain.

Other aspects
An electronic device is provided comprising a flexible copper clad laminate film according to the foregoing.
Yet another aspect
providing a non-conductive polymeric substrate;
forming a nickel-containing electroless plating layer on at least one surface of the non-conductive polymer substrate;
forming a copper electroless plated layer on one surface of the nickel-containing electroless plated layer to prepare the flexible copper clad film.

The flexible copper clad laminate film of the present invention is a film using an electroless plating layer for plating a metal in an aqueous solution state without thermal damage, and may have improved crystallinity and dimensional stability.

1 is a schematic diagram of a flexible copper clad laminate film according to one embodiment; FIG. FIG. 4 shows XRD (X-ray diffraction) analysis results for the flexible copper foil laminate film according to Example 1. FIG. 1 is a drawing showing a sample in which the flexible copper clad laminate film according to Example 1 is cut into a size of 295 mm×235 mm and 8 standard points are indicated. FIG. 3B is a view showing a method of measuring the distance between the standard points on the sample of FIG. 3A with a three-dimensional measuring device; FIG.

A flexible copper clad laminate (FCCL), an electronic device including the same, and a method for manufacturing the flexible copper clad laminate will be described in detail with reference to embodiments and drawings of the present invention. It should be understood by those skilled in the art that the examples are merely presented by way of illustration to further illustrate the present invention, and that the scope of the present invention is not limited by these examples. will be obvious to those skilled in the art.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, suitable methods and materials are described herein.

As used herein, the phrase "at least one side" in front of a component is meant to include both "one side" or "both sides" of said component. As used herein, the phrases "at least one," "one or more," or "one or more" in front of a component complement the list of the overall component and separate the individual components described above. It is not meant to be complementary.

As used herein, the term "and/or" is meant to include any and all combinations of one or more of the associated listed items. As used herein, the term "or" means "and/or."

As used herein, the term "comprising" does not exclude other components, unless specifically stated to the contrary, to indicate that other components may be added and/or interposed. used for The term "combinations thereof" is used herein to indicate mixtures, alloys, etc. of two or more of the previously described components. In this specification, the term "-based resin" is used to indicate a broad concept including "-resin" and/or "derivatives of -resin". The term "phosphorus flame retardant" is used herein to indicate a broad concept of flame retardants containing phosphorus.

In this specification, unless otherwise specified, the unit "parts by weight" means the weight ratio between each component.

As used herein, when a component is referred to as being positioned "on" another component, the component may be positioned directly on the other component or between the components. There may be intervening components. On the other hand, when a component is referred to as being placed "directly on" another component, there are no intervening components.

A flexible copper clad laminate film produced by a sputtering process suffers from thermal damage on the surface and has limited workability. In order to solve the above problems, the inventors of the present invention propose the following flexible copper foil laminate film.

A flexible copper clad laminate film according to one embodiment includes a non-conductive polymer substrate, a nickel-containing plating layer located on at least one surface of the non-conductive polymer substrate, and a copper layer located on the nickel-containing plating layer. and a plated layer, and the copper plated layer has an X-ray diffraction (XRD) spectrum, even if the half-value width fluctuation rate calculated by the following formula 1 related to the peak of the (111) plane is 0.01 ° or less. be.

FIG. 1 is a schematic diagram of a flexible copper clad laminate film 10 according to one embodiment.

Referring to FIG. 1 , the flexible copper clad laminate film 10 according to one embodiment shows a double-sided flexible copper clad laminate film 10 . In the flexible copper clad laminate film 10, nickel-containing plating layers 2, 2' and copper plating layers 3, 3' are sequentially arranged on both sides of a non-conductive polymer substrate 1, respectively.

The flexible copper clad laminate film 10 according to one embodiment may have a half-value width fluctuation rate of 0.01° or less and may have excellent crystallinity. Accordingly, the flexible copper clad laminate film 10 according to one embodiment may have improved dimensional stability. The copper plating layer also has a half width of 0.20 to 0.35° for the peak of the (111) plane in the X-ray diffraction spectrum. This can be confirmed from FIG. 2 and Analysis Example 1, which will be described later.

The non-conductive polymer substrate 1, the nickel-containing plated layers 2, 2' and the copper plated layers 3, 3', which constitute the flexible copper clad laminate film 10, will now be described in detail.

<Non-conductive polymer substrate 1>

The non-conductive polymer substrate 1 is at least one selected from phenol-based resins, phenol-aldehyde-based resins, allyl-based resins, epoxy-based resins, polyethylene-based resins, polypropylene-based resins, polyester-based resins, and polyimide-based resins. but also

For example, the non-conductive polymer substrate 1 may be made of a polyimide-based resin in consideration of adhesive strength, tensile strength and peel strength. For example, the polyimide-based resin is prepared by extruding a polyamic acid, which is a polyimide precursor, to form a film, and heat-treating the film for imidization of the polyamic acid. Material 1 can be manufactured.

The non-conductive polymer substrate 1 can be dried by methods commonly used in the art to remove moisture and residual gas. For example, under normal pressure, it may be performed through a roll to roll type heat treatment, or it may be performed using an infrared (IR) heater under a vacuum atmosphere.

The thickness of said non-conducting polymer substrate 1 is also 5-100 μm, for example 10-40 μm, or even 20-30 μm. The non-conductive polymer base material 1 can provide a base material having excellent flexibility and adhesive strength while blocking thermal damage within the above thickness range.

<Nickel-containing plated layers 2, 2'>

Sputtering type plasma treatment can ensure adhesion between the non-conductive polymer substrate 1 and the copper plating layers 3, 3', but the thin-film type non-conductive polymer substrate 1 having a thickness of 25 μm or less is Thermal damage can occur during processing. Such thermal damage can significantly change the dimensions of the non-conducting polymeric substrate 1 .

In order to solve such problems, the nickel-containing plating layers 2 and 2' are also electroless plating layers formed by an electroless plating method in which metal is deposited in an aqueous solution. The nickel-containing plating layers 2, 2' may include a nickel layer. If necessary, the nickel-containing plating layer may include a nickel alloy layer. The nickel alloy layer may contain, for example, Ni and one or more selected from Cr, Mo and Nb. The electroless plated layer may prevent thermal damage and improve dimensional stability with respect to the non-conductive polymer substrate 1 .

The nickel-containing plating layers 2, 2' are also formed by electroless plating using the following plating solution, for example. As the electroless plating method, both horizontal electroless plating method and/or vertical electroless plating method can be used.

The plating solution may contain a water-soluble nickel salt, a reducing agent and a complexing agent, and the water-soluble nickel salt includes nickel sulfate, nickel chloride, nickel hypophosphite, nickel acetate, nickel malate, and their water. It may contain one or more selected from Japanese foods. The water-soluble nickel salt is also contained in the plating solution at a concentration of 3 to 50 g/l, such as 3 to 35 g/l, such as 3 to 15 g/l. Within the above range, the water-soluble nickel salt improves the deposition rate and fluidity of the nickel plating film, and reduces the occurrence of pits in the nickel plating film.

As the reducing agent, a reducing agent commonly used in the art can be used. For example, the reducing agent may be a hypophosphite such as sodium hypophosphite, potassium hypophosphite; a borohydride compound such as sodium borohydride, potassium borohydride; dimethylamine borane (DMAB). , trimethylamine borane, amine borane compounds such as triethylamine borane;

The concentration of the reducing agent contained in the plating solution varies depending on the type of reducing agent used. For example, when using sodium hypophosphite as a reducing agent, the concentration is also 20 to 50 g/l. For example, when the boron compound dimethylamine borane (DMAB) is used as the reducing agent, the concentration is 1 to 10 g/l, such as 3 to 5 g/l. Within the concentration range, it is possible to prevent the problem of requiring a long period of time for decomposition of the plating solution or film formation.

In addition, the plating solution may further contain a complexing agent to prevent precipitation of the nickel compound and control the nickel deposition reaction.

Said complexing agents include dicarboxylic acids such as malic acid, succinic acid, tartaric acid, malonic acid, oxalic acid, adipic acid; aminocarboxylic acids such as glycine, glutamic acid, aspartic acid, alanine; ethylenediaminetetraacetic acid (EDTA); Ethylenediamine derivatives such as Versenol (N-hydroxyethylethylenediamine-N,N',N'-triacetic acid), Qudrol (N,N,N',N'-tetrahydroxyethylethylenediamine); 1-hydroxyethane-1, phosphonic acids such as 1-diphosphonic acid, ethylenediaminetetramethylene phosphonic acid; and soluble salts thereof.

The complexing agent may be included in the plating solution at a concentration of 0.001 to 2 mol/l, for example, 0.002 to 1 mol/l. The complexing agent can prevent the decomposition of the plating solution and the precipitation of nickel hydroxide within the concentration range.

Also, the plating solution may further include a sulfur-containing benzothiazole-based compound represented by Formula 1 below.

（ここで、Ｘは、ハロゲン原子、Ｃ_１－Ｃ_１０アルコキシ基、Ｃ_２－Ｃ_１０アルコキシアルキル基、Ｃ_１－Ｃ_１０ヘテロアルキル基、Ｃ_６－Ｃ_２０アリール基、Ｃ_６－Ｃ_２０アリールアルキル基、Ｃ_６－Ｃ_２０ヘテロアリール基またはＣ_７－Ｃ_２０ヘテロアリールアルキル基で置換もしくは非置換のＣ_２－Ｃ_３０アルキル基、またはその塩である）

(wherein X is a halogen atom, C ₁ -C ₁₀ alkoxy group, C ₂ -C ₁₀ alkoxyalkyl group, C ₁ -C ₁₀ heteroalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl a C ₂ -C ₃₀ alkyl group substituted or unsubstituted with an alkyl group, a C ₆ -C ₂₀ heteroaryl group or a C ₇ -C ₂₀ heteroarylalkyl group, or a salt thereof)

"Halogen atom" includes fluorine, bromine, chlorine, iodine, and the like.

"Alkyl" refers to a fully saturated branched or unbranched (alternatively straight or linear) hydrocarbon. Non-limiting examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, iso-amyl, n-hexyl, 3- Examples include methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl and n-heptyl.

"Alkoxy" means an alkyl attached to an oxygen atom.

"Aryl" also includes groups in which an aromatic ring is fused to one or more carbocyclic rings. Non-limiting examples of "aryl" include phenyl, naphthyl or tetrahydronaphthyl and the like.

"Heteroaryl" refers to a monocyclic or bicyclic organic compound containing one or more heteroatoms selected from N, O, P or S and wherein the remaining ring atoms are carbon. means. The heteroaryl group may contain, for example, 1-5 heteroatoms and may contain 5-10 ring members. The S or the N can be oxidized and have various oxidation states.

Non-limiting examples of "heteroaryl" include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl , 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl , isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol- 5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5- yl, tetrazolyl, pyrid-2-yl, pyrid-3-yl, 2-pyrazin-2-yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl yl or 5-pyrimidin-2-yl.

The concentration of the sulfur-containing benzothiazole-based compound in the plating solution is also 0.1 to 1 g/l. The sulfur-containing benzothiazole-based compound can provide improved film flexibility within the concentration range.

Also, the plating solution may further contain a stabilizer. The stabilizer may include Pb compounds such as lead acetate, inorganic compounds such as Bi compounds such as bismuth acetate; organic compounds such as butynediol; can be used

The electroless nickel plating solution also has a pH of 4-8. For example, the electroless nickel plating solution may have a pH of 4 to 7.5. The electroless nickel plating solution can obtain a stable deposition rate within the pH range while preventing decomposition of the plating solution.

The thickness of said nickel-containing plating layer 2, 2' is also between 40 nm and 250 nm, for example between 40 nm and 200 nm, or between 40 nm and 150 µm. The nickel-containing plated layers 2 and 2 ′ can be easily plated within the thickness range and have improved dimensional stability with respect to the non-conductive polymer substrate 1 .

<Copper plating layers 3, 3'>

The copper plating layers 3 and 3' are also electroless plating layers formed by electroless plating in which metal is deposited in an aqueous solution in the same manner as the nickel-containing plating layers 2 and 2'.

The copper plating layers 3 and 3' are also formed through an electroless plating method using, for example, the following plating solution and method.

The electroless plating is also performed through methods commonly used in the art. The electroless plating can be either a horizontal electroless plating method or/and a vertical electroless plating method.

The plating solution may include a source of copper ions, a complexing or chelating agent, a reducing agent, water, optionally one or more surfactants, and optionally one or more pH adjusting agents.

The sources of copper ions may include, but are not limited to, water-soluble halides, nitrates, acetates, sulfates, and other organic and airless salts of copper. The sources of copper ions can be used alone or in combination to provide copper ions. The source of copper ions may include, for example, copper sulfate, copper sulfate pentahydrate, copper chloride, copper nitride, copper hydroxide, copper sulfamate, or combinations thereof. The source of copper ions is from 0.5 g/l to 30 g/l, such as from 1 g/l to 25 g/l, such as from 5 g/l to 20 g/l, such as from 5 g/l to 15 g/l, such as It is also contained in the plating solution at a concentration of 10g/l to 15g/l.

The complexing agent or the chelating agent includes sodium potassium tartrate, sodium tartrate, sodium salicylate, sodium salt of ethylenediaminetetraacetic acid, nitriloacetic acid and its alkali metal salts, gluconic acid, gluconate, triethylalcoholamine, modified ethylenediamine tetraacetic acid. It may include, but is not limited to, acetic acid, S,S-ethylenediamine disuccinic acid, hydantoin and hydantoin derivatives, or combinations thereof. Said hydantoin derivatives may include, but are not limited to, 1-methylhydantoin, 1,3-dimethylhydantoin and 5,5-dimethylhydantoin. The complexing agent is between 10 g/l and 150 g/l, such as between 20 g/l and 150 g/l, such as between 30 g/l and 100 g/l, such as between 35 g/l and 80 g/l, and such as between 35 g/l and It is also contained in the plating solution at a concentration of 1 to 55 g/l. The reducing agents include formaldehyde, formaldehyde precursors, formaldehyde derivatives such as paraformaldehyde; borohydrides such as sodium borohydride, substituted borohydrides; boranes such as dimethylamine borane (DMAB); sugars such as glucose (glucose ), glucose, sorbitol, cellulose, sugar cane sugar, mannitol and gluconolactone; hypophosphites and their salts, such as sodium hypophosphite; hydroquinone; catechol; gallic; 3,4-dihydroxybenzoic acid; phenolsulfonic acid; cresolsulfonic acid; hydroquinonesulfonic acid; catecholsulfonic acid; not to be The reducing agent may be from 0.5 g/l to 100 g/l, such as from 0.5 g/l to 60 g/l, such as from 1 g/l to 50 g/l, such as from 1 g/l to 20 g/l, such as 1 g /l to 10 g/l, such as 1 g/l to 5 g/l, in the plating solution.

The pH of the plating solution is also greater than 7. Optionally, one or more pH adjusting agents may be included in the plating solution to adjust the pH of the plating solution to an alkaline pH. The pH modifier may comprise organic acids, inorganic acids, organic bases, inorganic bases, or mixtures thereof. For example, the inorganic acid may include phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or combinations thereof. For example, the inorganic base may include ammonium hydroxide, sodium hydroxide, potassium hydroxide, or combinations thereof.

Optionally, one or more surfactants are also included in the plating solution. Such surfactants may include ionic, such as cationic and anionic surfactants, nonionic and amphoteric surfactants. The surfactants may be used alone or as a mixture thereof. The surfactant is also contained in the plating solution at a concentration of 0.001 g/l to 50 g/l, such as 0.01 g/l to 50 g/l. Said cationic surfactants may include tetraalkylammonium halides, alkyltrimethylammonium halides, hydroxyethylalkylimidazolines, alkylbenzalkonium halides, alkylamine acetates, alkylamine oleates and alkylaminoethylglycine, although these is not limited to The anionic surfactants include alkylbenzene sulfonates, alkylnaphthalene sulfonates or alkoxynaphthalene sulfonates, alkyldiphenyl ether sulfonates, alkyl ether sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenol ether sulfates, and higher alcohols. Phosphorus monoesters, polyoxyalkylene alkyl ether phosphates (phosphates) and alkyl sulfosuccinates may include, but are not limited to. The nonionic surfactants include alkylphenoxypolyethoxyethanols having 20 to 150 repeating units, polyoxyethylene polymers, and random and block copolymers of polyoxyethylene and polyoxypropylene. However, it is not limited to them. Said amphoteric surfactant is methyl 2-alkyl-N-carboxylate, ethyl-N-hydroxyethyl or methylimidazolinium betaine; methyl 2-alkyl-N-carboxylate or ethyl-N-carboxymethyloxyethylimidazol dimethylalkylbetaine, N-alkyl-β-aminopropionic acid or salts thereof; and fatty acid amidopropyldimethylaminoacetate betaine, but are not limited thereto.

The thickness of said copper plating layer 3, 3' is also between 40 nm and 150 nm, for example between 50 nm and 140 nm, or between 60 nm and 140 µm. The copper plating layers 3 and 3 ′ can be easily plated within the above thickness range, and can improve the dimensional stability with respect to the non-conductive polymer substrate 1 .

In this specification, the thickness of each layer can be measured by a general method in the technical field. For example, the thickness of each layer can be measured using X-ray fluorescence (XRF) analysis. The X-ray fluorescence analysis method irradiates a target substance with primary X-rays having a certain energy, and emits specific X-rays while outer electrons move to electron positions emitted by excitation from the inside of the substance. This is a method of analyzing by detecting the magnitude of energy and utilizing the principle that the energy intensity differs depending on the plating thickness.

<Flexible copper foil laminate film 10>

After leaving the flexible copper foil laminate film for 1 to 60 days, it is heat-treated at 150° C. for 30 minutes. is also 0.015 or less.

The "initial dimension" means the average value obtained by displaying a plurality of standard points on a sample cut into a predetermined size and measuring the distance between the plurality of standard points. "Dimensions after measurement" is the average value obtained by measuring the distance between the plurality of standard points after leaving the sample on which the plurality of standard points are displayed for 1 to 60 days, followed by heat treatment at 150 ° C. for 30 minutes. means.

<Electronic element>

The electronic device may include the flexible copper foil laminate film described above. The electronic elements may include, for example, electronic circuit elements or electronic components. The electronic circuit element may include, for example, a semiconductor, a printed circuit board, or a wiring board. Said electronic device may for example comprise a display device such as an LCD, OLED.

<Method for producing flexible copper foil laminate film 10>

A method for manufacturing a flexible copper clad laminate film according to one embodiment includes the steps of preparing a non-conductive polymer substrate and forming a nickel-containing electroless plating layer on at least one surface of the non-conductive polymer substrate. and forming a copper electroless plating layer on one surface of the nickel-containing electroless plating layer to produce the flexible copper clad laminate film.

The step of preparing the non-conductive polymeric substrate may further include a drying step to remove moisture and residual gas from the non-conductive polymeric substrate.

The drying step is performed, for example, at 50-300° C., for example, 60-280° C., or even 70-270° C., using an infrared (IR) heater in a vacuum atmosphere. Within the drying temperature range, moisture can be properly removed without damaging the non-conductive polymer substrate and deteriorating its quality.

The step of forming the nickel-containing electroless plating layer may form the nickel-containing plating layer using a wet electroless plating method.

The wet electroless plating method is not limited in terms of plating conditions and plating equipment, and can be performed by appropriately selecting a general method. For example, the electroless nickel-containing plating solution having the above composition can be immersed in or brought into contact with the object to be plated. At this time, the plating temperature is also 45 to 90°C, for example, 47 to 87°C, or 50 to 85°C. The plating treatment time can be appropriately set depending on the thickness of the nickel plating film to be formed, and is, for example, 0.1 to 60 minutes, such as 0.5 to 10 minutes. A stable nickel-containing plating layer can be formed within the ranges of the plating temperature and the plating time.

In the step of forming the copper electroless plating layer and manufacturing the flexible copper clad film, the copper plating layer may be formed by a wet electroless plating method. The method for forming the copper plating layer is not limited in terms of plating conditions and plating equipment, and can be carried out by appropriately selecting a general method. For example, the electroless copper plating solution having the above composition can be immersed in or brought into contact with the object to be plated. At this time, the plating temperature is, for example, room temperature to about 50.degree. The plating treatment time can be appropriately set depending on the film thickness of the copper plating film to be formed, and is, for example, 0.1 to 60 minutes, or, for example, 0.5 to 30 minutes. A stable copper plating layer can be formed within the ranges of the plating temperature and the plating time.

Examples and comparative examples are described below. However, the following embodiment is only one embodiment of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope of the present invention and within the scope of the technical idea. It goes without saying that embodiments with such changes and modifications fall within the scope of the claims.

Example 1: Flexible copper foil laminate film

A polyimide film (Kapton 100ENC, manufactured by TDC) with a thickness of 25 μm was used as a non-conductive polymer substrate. Electroless nickel plating layers (thickness: about 100 nm) 2, 2' and electroless copper plating layers (thickness: about 100 nm) 3, 3' are formed on both sides of the polyimide film substrate 1 by horizontal electroless plating. They were formed in sequence, and as can be seen from FIG. 1, a flexible copper foil laminate film 10 was produced.

(Electroless nickel plating solution)

・Plating solution: Nickel salt hydrate NiSO ₄ .6H ₂ O is set so that the concentration of nickel ions is about 5 g/L ・Bath temperature: about 60°C
・Nickel deposition time: about 1 minute ・pH concentration: about 7.3
(Electroless copper plating solution)
・Plating solution: copper sulfate 16.25 ml/L, sulfuric acid 3.25 ml/L
・Bath temperature: 34℃
・Copper deposition time: about 2.5 minutes ・pH concentration: about 13.0

Comparative Example 1: Flexible copper foil laminate film

A polyimide film (Kapton 100ENC, manufactured by TDC) with a thickness of 25 μm was used as a non-conductive polymer substrate. A Ni—Cr alloy tie layer and a Cu seed layer were sequentially formed on one surface of the polyimide film substrate 1 by physical vapor deposition (PVD) using a roll-to-roll type sputtering apparatus. At this time, the tie layer has a weight ratio of Ni and Cr of 80:20 (purity: 99.9% or more) and is formed to a thickness of about 250 Å, and the Cu seed layer uses copper with a purity of 99.995%. and formed to a thickness of about 1,000 Å to produce a flexible copper foil laminate film.

Comparative Example 2: Flexible copper foil laminated film

A copper plating layer having a thickness of about 4 μm was formed on the copper seed layer by electroplating using a copper sulfate plating solution. At this time, the plating solution used was a solution containing about 26 g/L of Cu ²⁺ and about 188 g/L of sulfuric acid. At a bath temperature of about 30° C., a current was applied at a current density of about 1.7 A/dm ² to form a copper electroplating layer with a thickness of about 4 μm to produce a flexible copper foil laminate film. A flexible copper foil laminate film was produced in the same manner as in Comparative Example 1.

Analysis example 1: XRD (X-ray diffraction) analysis

An XRD analysis experiment was performed on the flexible copper foil laminate films according to Example 1, Comparative Example 1, and Comparative Example 2, respectively. The XRD analysis utilized a Cu K-alpha characteristic X-ray wavelength of 1.541 Å. As can be seen from FIG. 2, in the flexible copper foil laminate film according to Example 1, a peak of the (111) plane was observed at a Bragg 2θ angle of 43°. After leaving the flexible copper foil laminate films according to Example 1, Comparative Examples 1 and 2 for 60 days, the half maximum width (FWHM) obtained from the peak of the (111) plane was calculated by the following Equation 1. We calculated the price fluctuation rate. The results are shown in Table 1 below.

Referring to Table 1, after the flexible copper clad laminate film according to Example 1 was left for 60 days, the half-value width fluctuation rate related to the peak of the (111) plane remained almost unchanged at 0.01. The soft copper foil laminate films according to 1 and 2 had slight changes of 0.095 and 0.024. As a result, it can be seen that the flexible copper foil laminate film according to Example 1 has improved crystallinity as compared with the flexible copper foil laminate films according to Comparative Examples 1 and 2.

Analysis example 2: Dimensional stability analysis

The polyimide base films of the flexible copper foil laminate films according to Example 1, Comparative Example 1 and Comparative Example 2 were analyzed for 60-day dimensional stability. The results are shown in Table 2 below.

The dimensional stability was analyzed by the following method.

Samples were prepared by cutting the flexible copper foil laminate films according to Example 1, Comparative Example 1, and Comparative Example 2 into a size of 295 mm×235 mm. Eight standard points were displayed for the samples (Fig. 3A). The distance between the standard points was measured with a three-dimensional measuring device (Fig. 3B), and the average value (initial dimension) was obtained. Eight points corresponding to the standard points were punched on the surface of the polyimide base film of the sample, and the sample was left in a constant temperature and humidity room (23±2° C., 50±5%) for 1 to 60 days. After that, the sample was heat-treated at 150° C. for 30 minutes, left in a constant temperature and humidity room for 24 hours, and then measured with a three-dimensional measuring device to measure the distances between the eight points corresponding to the standard points for the polyimide base film. Then, an average value (dimension after standing for 1 to 60 days) was obtained, and the value obtained by subtracting the minimum dimension from the maximum dimension was taken as the dimensional change rate.

Referring to Table 2, it can be seen that the dimensional change rate of the flexible copper clad film according to Example 1 with respect to the polyimide base film was 0.014. It can be confirmed that the dimensional change ratio of the film to the polyimide base film is 0.018 and 0.017, respectively. As a result, it can be seen that the flexible copper clad laminate film according to Example 1 has superior dimensional stability for 60 days to the polyimide base film compared to the flexible copper clad laminate films according to Comparative Examples 1 and 2. .

REFERENCE SIGNS LIST 1 non-conductive polymeric substrate 2 nickel-containing plating layer 2' nickel-containing plating layer 3 copper plating layer 3' copper plating layer 10 flexible copper foil laminate film

Claims (8)

a non-conductive polymeric substrate;
a nickel-containing plating layer located on at least one surface of the non-conductive polymer substrate;
A flexible copper foil laminate film comprising a copper plating layer located on the nickel-containing plating layer,
The nickel-containing plating layer and the copper plating layer are electroless plating layers,
In the X-ray diffraction spectrum, the copper plating layer has a half-value width fluctuation rate of 0.01° or less, which is calculated by the following formula 1 related to the peak of the (111) plane,
Half-value width (111) fluctuation rate = {(half-value width after leaving for 60 days)-(initial half-value width)} ... Equation 1
and
Cut the flexible copper foil laminate film into a size of 295 mm × 235 mm, mark 8 points in the cut flexible copper foil laminate film, measure the distance between the 8 points to obtain the initial size, After standing for 1 to 60 days at constant temperature (23±2° C.) and constant humidity (50±5%), heat treatment at 150° C. for 30 minutes and leave for 24 hours, then measure the distance between the eight points. The non-conductive polymer, which is the value obtained by subtracting the minimum value from the maximum value of the initial dimension value and the value of each dimension after being left for 1 to 60 days. A flexible copper foil laminate film in which the dimensional change rate of the substrate is 0.015 or less . 2. The flexible copper clad laminate film according to claim 1, wherein the copper plating layer has a half width of 0.20 to 0.35° for the peak of the (111) plane in the X-ray diffraction spectrum. 2. The flexible copper foil laminate film according to claim 1, wherein the copper plating layer has a thickness of 40 nm to 150 nm. 2. The flexible copper foil laminate film according to claim 1, wherein said nickel-containing plating layer comprises a nickel layer. 2. The flexible copper foil laminate film according to claim 1, wherein the nickel-containing plating layer has a thickness of 40 nm to 250 nm. The non-conductive polymer base material is one or more selected from phenolic resins, phenolaldehyde-based resins, allyl-based resins, epoxy-based resins, polyethylene-based resins, polypropylene-based resins, polyester-based resins, and polyimide-based resins. The flexible copper foil laminate film of claim 1, comprising: An electronic device comprising the flexible copper foil laminate film according to any one of claims 1 to 6 . providing a non-conductive polymeric substrate;
forming a nickel-containing electroless plating layer on at least one surface of the non-conductive polymer substrate;
forming a copper electroless plating layer on one surface of the nickel-containing electroless plating layer to manufacture the flexible copper foil laminate film according to any one of claims 1 to 6 . A method for producing a laminated film.

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