KR102319385B1 - Flexible copper clad laminate, electronic device including the same, and method for manufacturing the flexible copper clad laminate - Google Patents

Abstract

A flexible copper-clad laminated film, an electronic device including the same, and a method for manufacturing the flexible copper-clad laminated film are disclosed. The flexible copper foil laminated film is a non-conductive polymer substrate; a nickel-containing plating layer located on at least one surface of the substrate; a copper plating layer positioned on the nickel-containing plating layer; and the copper plating layer may have a fluctuation rate of half maximum width calculated by Equation 1 for a peak of (111) plane in an X-ray diffraction spectrum of 0.01° or less.
<Equation 1>
Width at half maximum (111) Change rate = {(width at half maximum after leaving for 60 days) - (initial width at half maximum)}

Description

Flexible copper clad laminate, electronic device including the same, and method for manufacturing the flexible copper clad laminate

It relates to a flexible copper-clad laminated film, an electronic device including the same, and a manufacturing method of the flexible copper-clad laminated film.

As the growth of the mobile market accelerates and the demand for LCD TV monitors increases, the development of materials having characteristics of thin film, miniaturization, weight reduction, durability and high quality in the fields of electronic products and semiconductor integrated circuits is being promoted. In the field of flexible copper clad laminated film (FCCL) used in driver integrated circuits (ICs) for LCDs, fine patterning, thinning and durability are increasingly required.

The flexible copper clad laminated film (FCCL) has a structure in which a circuit pattern is formed on the surface and an electronic device such as a semiconductor chip is mounted on the circuit pattern. Recently, the number of products having a pitch of the circuit pattern of 23 μm or less is increasing, and the instability of dimensional change is a problem due to a downward trend in pitch and line width.

In order to solve this problem, a fine circuit pattern forming technology is also being developed. However, for fine circuit patterning, high adhesion between the substrate and the metal layer must be maintained, and the problem of interlayer peeling of the flexible copper clad laminated film (FCCL) must be solved.

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

One aspect is to provide a flexible copper clad laminated film having improved crystallinity and dimensional stability.

Another aspect is to provide an electronic device including the flexible copper clad laminated film.

Another aspect is to provide a method of manufacturing the flexible copper foil laminated film.

According to one aspect,

non-conductive polymeric substrates;

a nickel-containing plating layer located on at least one surface of the substrate;

and a copper plating layer positioned on the nickel-containing plating layer;

The copper plating layer is provided with a flexible copper clad laminated film having a half-width variation of 0.01° or less calculated by Equation 1 below with respect to the peak of the (111) plane in the X-ray diffraction spectrum.

In the X-ray diffraction spectrum, the copper plating layer may have a full width at half maximum with respect to the peak of the (111) plane of 0.20 to 0.35°.

Each of the nickel-containing plating layer and the copper plating layer may be an electroless plating layer.

The thickness of the copper layer may be 40 nm to 150 nm.

After leaving the flexible copper clad laminated film for 1 to 60 days, heat treatment at 150° C. for 30 minutes may result in a dimensional change rate of 0.015 or less for the substrate, which is a value obtained by subtracting the smallest dimension from the largest dimension among the dimensions.

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

The thickness of the nickel-containing plating layer may be 40 nm to 250 nm.

The non-conductive polymer substrate may include at least one selected from a phenol-based resin, a phenolaldehyde-based resin, an allyl-based resin, an epoxy-based resin, a polyethylene-based resin, a polypropylene-based resin, a polyester-based resin, and a polyimide-based resin. can

According to the other aspect,

An electronic device comprising the flexible copper clad laminated film according to the above is provided.

According to another aspect,

preparing a non-conductive polymer substrate;

forming a nickel-containing electroless plating layer on at least one surface of the substrate; and

Forming a copper electroless plating layer on one surface of the nickel-containing electroless plating layer to prepare the above-described flexible copper foil laminated film; is provided a method of manufacturing a flexible copper foil laminated film comprising a.

The flexible copper clad laminated film according to one aspect is a film using an electroless plating layer for plating a metal in an aqueous solution state without thermal damage, and crystallinity and dimensional stability can be improved.

1 is a schematic diagram of a flexible copper clad laminated film according to an embodiment.
2 is an XRD analysis result of the flexible copper clad laminated film according to Example 1. FIG.
Figure 3 (a) is a sample in which the flexible copper clad laminated film according to Example 1 is cut to a size of 295 mm x 235 mm and marked with eight standard points, Figure 3 (b) is a three-dimensional measuring instrument to measure the distance between the standard points shows how to do it.

A flexible copper clad laminated film, an electronic device including the same, and a method of manufacturing the flexible copper clad laminated film will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those of ordinary skill in the art that these examples are only presented by way of example to explain the present invention in more detail, and that the scope of the present invention is not limited by these examples. .

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 be used in the practice or testing of the present invention, suitable methods and materials are described herein.

In the present specification, the expression “at least one side” in front of a component means including both “one side” or “both sides” of the component. The expression "at least one", "one or more", or "one or more" in front of elements in the present specification means that it may supplement the list of all elements and may supplement individual elements of the description. I never do that.

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

In the present specification, the term “including” is used to indicate that other components may be added and/or interposed, rather than excluding other components, unless specifically stated otherwise. In the present specification, the term “combination of these” is used to indicate a mixture or alloy of two or more components described above. In the present specification, the term "-based resin" is used to denote a broad concept including "-resin" or/and "derivatives of-resin". The term "phosphorus-based flame retardant" is used herein to denote the broad concept of a flame retardant comprising phosphorus.

Unless otherwise specified in the specification, the unit "part by weight" means a weight ratio between each component.

When it is referred to in this specification that one component is disposed "on" another component, one component may be disposed directly on the other component or there may be components interposed between the components. have. On the other hand, when an element is referred to as being disposed "directly on" another element, intervening elements may not exist.

The flexible copper clad laminated film manufactured by the sputtering process has thermal damage on its surface, which limits workability. The inventors of the present invention intend to propose the following flexible copper foil laminated film in order to solve the above problem.

A flexible copper foil laminated film according to an embodiment includes a non-conductive polymer substrate; a nickel-containing plating layer located on at least one surface of the substrate; may include; a copper plating layer positioned on the nickel-containing plating layer, wherein the copper plating layer has a fluctuation rate of half maximum width calculated by Equation 1 below for a peak of a (111) plane in an X-ray diffraction spectrum of 0.01° or less. :

<Equation 1>

Width at half maximum (111) change rate = {(width at half maximum after leaving for 60 days) - (initial width at half maximum)}

1 is a schematic diagram of a flexible copper clad laminated film 10 according to an embodiment.

Referring to FIG. 1 , a flexible copper foil laminated film 10 according to an embodiment shows a double-sided flexible copper foil laminated film 10 . In the flexible copper clad laminated film 10 , nickel-containing plating layers 2 and 2 ′ and copper plating layers 3 and 3 ′ are sequentially disposed on both surfaces of the non-conductive polymer substrate 1 , respectively.

Flexible copper clad laminated film 10 according to an embodiment may have a half-width variation of 0.01° or less, and may have excellent crystallinity. For this reason, the flexible copper clad laminated film 10 according to an embodiment may have improved dimensional stability. In the X-ray diffraction spectrum, the copper plating layer may have a full width at half maximum with respect to the peak of the (111) plane of 0.20 to 0.35°. This can be confirmed from FIG. 2 and Analysis Example 1 to be described later.

Hereinafter, each of the non-conductive polymer substrate 1, the nickel-containing plating layers 2 and 2', and the copper plating layers 3 and 3' constituting the flexible copper clad laminated film 10 will be described in detail.

< non-conductive Polymer substrate (1)>

The non-conductive polymer substrate 1 may be at least one selected from a phenol-based resin, a phenolaldehyde-based resin, an allyl-based resin, an epoxy-based resin, a polyethylene-based resin, a polypropylene-based resin, a polyester-based resin, and a polyimide-based resin. can

For example, the non-conductive polymer substrate 1 may include a polyimide-based resin in consideration of adhesive strength, tensile strength, peel strength, and the like. For example, the polyimide-based resin is produced by extruding polyamic acid, which is a polyimide precursor, to make a film, and heat-treating the film for imidization of the polyamic acid to prepare the polyimide-based resin-containing non-conductive polymer substrate (1). can

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

The thickness of the non-conductive polymer substrate 1 may be 5 to 100 μm, for example, 10 to 40 μm or 20 to 30 μm. The non-conductive polymer substrate 1 may obtain a substrate having excellent ductility and adhesion while blocking thermal damage within the thickness range.

<Contains nickel plating layer (2, 2')>

The sputtering plasma treatment can secure the adhesion between the non-conductive polymer substrate 1 and the copper plating layers 3 and 3', but thermal damage during processing of the thin film type non-conductive polymer substrate 1 of 25 μm or less. This can happen. According to such thermal damage, the dimensions of the non-conductive polymer substrate 1 may be significantly changed.

In order to solve this problem, the nickel-containing plating layers 2 and 2' may be an electroless plating layer formed by an electroless plating method of depositing a metal in an aqueous solution state. The nickel-containing plating layers 2 and 2' may include a nickel layer. If necessary, the nickel-containing plating layer may include a nickel alloy layer. The nickel alloy layer may include, for example, Ni and at least one selected from Cr, Mo, and Nb. The electroless plating layer may have improved dimensional stability of the non-conductive polymer substrate 1 while preventing thermal damage.

The nickel-containing plating layers 2 and 2' may be formed through, for example, an electroless plating method using the following plating solution. The electroless plating method may be used in both horizontal and/or vertical electroless plating methods.

The plating solution may include a water-soluble nickel salt, a reducing agent, and a complexing agent, and the water-soluble nickel salt may include at least one selected from nickel sulfate, nickel chloride, nickel hypophosphite, nickel acetate, nickel malate, and hydrates thereof. have. The water-soluble nickel salt may be included in the plating solution at a concentration of 3 to 50 g/L, for example, 3 to 35 g/L, for example, 3 to 15 g/L. The water-soluble nickel salt may improve the deposition rate and fluidity of the nickel plating film within the above range, and may reduce the occurrence of pits in the nickel plating film.

The reducing agent may be a reducing agent commonly used in the art. For example, the reducing agent is hypophosphite, such as sodium hypophosphite and potassium hypophosphite; boron hydride compounds such as sodium borohydride and potassium borohydride; amine borane compounds such as dimethylamine borane (DMAB), trimethylamine borane, and triethylamine borane; and the like.

The concentration of the reducing agent contained in the plating solution may be different depending on the type of the reducing agent used. For example, when sodium hypophosphite is used as a reducing agent, the concentration may be 20 to 50 g/L. For example, when dimethylamine boron (DMAB), a boron compound, is used as the reducing agent, the concentration may be 1 to 10 g/L, for example, 3 to 5 g/L. Within the above concentration range, it is possible to prevent the decomposition of the plating solution or the problem of requiring a long time to form a film.

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

The complexing agent may include dicarboxylic acids such as malic acid, succinic acid, tartaric acid, malonic acid, oxalic acid, and adipic acid; aminocarboxylic acids such as glycine, glutamic acid, aspartic acid, and alanine; Ethylenediaminetetraacetic acid, Versenol (N-hydroxyethylethylenediamine-N,N',N'-triacetic acid), Quadrol (N,N,N',N'-tetrahydroxyethylethylenediamine), etc. ethylenediamine derivatives of phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid; and these soluble salts.

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

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

<Formula 1>

(wherein X is a halogen atom, C1-C10 alkoxy, C2-C10 alkoxyalkyl, C1-C10 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 heteroaryl group, or a C2-C30 alkyl group unsubstituted or substituted with a C7-C20 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 (or 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 -methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, or n-heptyl etc. are mentioned.

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

Non-limiting examples of "heteroaryl" include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxa Diazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl group, 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-2yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl, or 5-pyrimidin-2-yl can be heard

The concentration of the sulfur-containing benzothiazole compound in the plating solution may be 0.1 to 1 g/L. The sulfur-containing benzothiazole-based compound may obtain improved film flexibility within the concentration range.

In addition, the plating solution may further include a stabilizer. Examples of the stabilizer include inorganic compounds such as Pb compounds such as lead acetate and Bi compounds such as bismuth acetate; organic compounds such as butynediol; and the like, and among them, it may be used alone or in combination of two or more.

The electroless nickel plating solution may have a pH of 4 to 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 while preventing decomposition of the plating bath within the pH range.

The thickness of the nickel-containing plating layer (2, 2') may be 40 nm to 250 nm, for example, may be 40 nm to 200 nm, or may be 40 nm to 150 ㎛. The nickel-containing plating layers 2 and 2' may be easily plated within the thickness range, and dimensional stability of the non-conductive polymer substrate 1 may be improved.

<Copper plating layer (3, 3')>

The copper plating layers 3 and 3' may be an electroless plating layer formed by an electroless plating method of depositing a metal in an aqueous solution in the same manner as the nickel-containing plating layers 2 and 2'.

The metal plating layers 4 and 4' may be formed through, for example, an electroless plating method using the following plating solution and method.

The electroless plating may be performed by a method commonly used in the art. For the electroless plating, both horizontal and/or vertical electroless plating methods may be used.

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

Sources of the copper ions may include, but are not limited to, water-soluble halides, nitrates, acetates, sulfates, and other organic and inorganic salts of copper. The source of copper ions may provide copper ions alone or in combination thereof. The copper ion source may include, for example, copper sulfate, copper sulfate pentahydrate, copper chloride, copper nitride, copper hydroxide, copper sulfamic acid, or a combination thereof. The source of copper ions is from 0.5 g/l to 30 g/l, for example from 1 g/l to 25 g/l, for example from 5 g/l to 20 g/l, for example from 5 g/l to 15 g/L, for example, may be included in the plating solution at a concentration of 10 g/L to 15 g/L.

The complexing or chelating agent is potassium sodium tartrate, sodium tartrate, sodium salicylate, sodium salt of ethylenediaminetetraacetic acid (EDTA), nitriloacetic acid and alkali metal salts thereof, gluconic acid, gluconate, triethanolamine, modified ethylenediaminetetra acetic acid, S, S-ethylenediamine disuccinic acid, hydantoin and hydantoin derivatives, or combinations thereof. The hydantoin derivative may include, but is not limited to, 1-methylhydantoin, 1,3-dimethylhydantoin, and 5,5-dimethylhydantoin. The complexing agent is from 10 g/l to 150 g/l, for example from 20 g/l to 150 g/l, for example from 30 g/l to 100 g/l, for example from 35 g/l to 80 g /L, and may be included in the plating solution at a concentration of, for example, 35 g/L to 55 g/L. The reducing agent is formaldehyde, formaldehyde precursors, formaldehyde derivatives such as paraformaldehyde; borohydrides such as sodium borohydride, substituted borohydride; boranes such as dimethylamine borane (DMAB); sugars such as glucose (glucose), glucose, sorbitol, cellulose, cane sugar, mannitol and gluconolactone; hypophosphite and salts thereof, such as sodium hypophosphite; hydroquinone; catechol; resorcinol; quinol; pyrogallol; hydroxyquinol; Phloroglucinol, Guaircol; gallic acid; 3,4-dihydroxybenzoic acid; phenolsulfonic acid; cresol sulfonic acid; hydroquinone sulfonic acid; catecholsulfonic acid; tyrone; and salts of all of the reducing agents described above, but are not limited thereto. The reducing agent is from 0.5 g/l to 100 g/l, for example from 0.5 g/l to 60 g/l, for example from 1 g/l to 50 g/l, for example from 1 g/l to 20 g/l. L, for example, 1 g/L to 10 g/L, for example, may be included in the plating solution at a concentration of 1 g/L to 5 g/L.

The pH of the plating solution may be greater than 7. Optionally, at least one pH adjusting agent may be included in the plating solution to adjust the pH of the plating solution to an alkaline pH. The pH adjusting agent may include an organic acid, an inorganic acid, an organic base, an inorganic base, or a mixture thereof. For example, the inorganic acid may include phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or a combination thereof. For example, the inorganic base may include ammonium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof.

Optionally, one or more surfactants may be included in the plating solution. Such surfactants may include ionic, for example, cationic and anionic surfactants, and nonionic and amphoteric surfactants. The surfactant may be used alone or a mixture thereof. The surfactant may be included in the plating solution at a concentration of 0.001 g/L to 50 g/L, for example, 0.01 g/L to 50 g/L. The cationic surfactant may include tetraalkylammonium halide, alkyltrimethylammonium halide, hydroxyethyl alkyl imidazoline, alkylbenzalkonium halide, alkylamine acetate, alkylamine oleate, and alkylaminoethyl glycine, but not limited The anionic surfactant is an alkylbenzene sulfonate, alkyl or alkoxy naphthalene sulfonate, alkyldiphenyl ether sulfonate, alkyl ether sulfonate, alkyl sulfuric acid ester, polyoxyethylene alkyl ether sulfuric ester, polyoxyethylene alkyl phenol ether sulfuric ester , higher alcohols phosphorus monoesters, polyoxyalkylene alkyl ethers phosphoric acid (phosphate) and alkyl sulfosuccinates. The nonionic surfactant may include, but is not limited to, alkyl phenoxy polyethoxyethanol having 20 to 150 repeating units, polyoxyethylene polymers, and random and block copolymers of polyoxyethylene and polyoxypropylene. does not The amphoteric surfactant is 2-alkyl-N-carboxymethyl or ethyl-N-hydroxyethyl or methylimidazolium betaine, 2-alkyl-N-carboxymethyl or ethyl-N-carboxymethyloxyethyl imidazolium betaine, dimethylalkyl betaine, N-alkyl-β-aminopropionic acid or salts thereof and fatty acid amidopropyl dimethylaminoacetic acid betaine.

The thickness of the copper plating layers 3 and 3' may be 40 nm to 150 nm, for example, 50 nm to 140 nm, or 60 nm to 140 μm. The copper plating layers 3 and 3' may be easily plated within the thickness range and dimensional stability of the non-conductive polymer substrate 1 may be improved.

In the present specification, the thickness of each layer may be measured by a method conventional in the art. For example, the thickness of each layer may be measured using X-ray fluorescence (XRF) analysis. The X-ray fluorescence analysis method irradiates a target material with primary X-rays having a certain energy, and detects the magnitude of specific X-ray energy emitted while the outer electrons are transferred to the electron positions emitted due to excitation in the inner shell of the material. Therefore, it is a method of analysis using the principle that the energy intensity varies depending on the thickness of the plating.

< Flexible copper foil Laminated film (10)>

After leaving the flexible copper foil laminated film for 1 to 60 days, heat treatment at 150° C. for 30 minutes may result in a dimensional change rate of 0.015 or less for the substrate, which is a value obtained by subtracting the smallest dimension from the largest dimension among the dimensions.

The “initial dimension” refers to an average value obtained by measuring the distance between the plurality of standard points by marking a plurality of standard points for a sample cut to a predetermined size, and the “dimension after leaving for 1 to 60 days” is It refers to an average value obtained by measuring the distance between the plurality of standard points after leaving the sample marked with the plurality of standard points to stand for 1 to 60 days, and then performing heat treatment at 150° C. for 30 minutes.

<Electronic device>

The electronic device may include the above-described flexible copper foil laminated film. The electronic device may include, for example, an electronic circuit device or an electronic component. The electronic circuit device may include, for example, a semiconductor, a printed circuit board, or a wiring board. The electronic device may include, for example, a display device such as LCD or OLED.

< Flexible copper foil Manufacturing method of laminated film 10>

A method of manufacturing a flexible copper clad laminate according to an embodiment includes the steps of preparing a non-conductive polymer substrate; forming a nickel-containing electroless plating layer on at least one surface of the substrate; and forming a copper electroless plating layer on one surface of the nickel-containing electroless plating layer to prepare the above-described flexible copper foil laminated film.

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

The drying step, for example, using an infrared (IR) heater in a vacuum atmosphere at 50 to 300 ℃, for example, may be 60 to 280 ℃ or may be performed at 70 to 270 ℃. Within the drying temperature range, there is an effect that moisture can be properly removed without damage to the non-conductive polymer substrate and deterioration of quality.

In the forming of the nickel-containing electroless plating layer, the nickel-containing plating layer may be formed by a wet electroless plating method.

The wet electroless plating method is not limited to plating conditions and plating equipment, and may be appropriately selected according to a conventional method. For example, it may be carried out by immersing or contacting the plating solution containing the electroless nickel of the composition to the object to be plated. At this time, the plating temperature may be 45 to 90 ℃, for example, may be 47 to 87 ℃ or may be 50 to 85 ℃. The plating treatment time may be appropriately set depending on the film thickness of the nickel plating film to be formed, but may be, for example, 0.1 to 60 minutes, for example, 0.5 to 10 minutes. It is possible to form a stable nickel-containing plating layer within the range of the plating treatment temperature and the plating treatment time.

In the step of forming the copper electroless plating layer to prepare the above-described flexible copper foil laminate 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 to plating conditions and plating apparatus, and may be appropriately selected according to a conventional method. For example, the electroless copper plating solution of the above composition may be immersed in or contacted with the object to be plated. At this time, the plating treatment temperature may be, for example, performed at a temperature of room temperature to about 50 ℃. The plating treatment time may be appropriately set depending on the thickness of the copper plating film to be formed, for example, 0.1 to 60 minutes, for example, 0.5 to 30 minutes. A stable copper plating layer may be formed within the range of the plating treatment temperature and plating time.

Hereinafter, an Example and a comparative example are described. However, the following examples are only one embodiment of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and the embodiments to which such changes and modifications are attached fall within the scope of the claims. It is also natural.

[Example]

Example One: Flexible copper foil laminated film

A polyimide film (Kapton 100ENC, manufactured by TDC) having a thickness of 25 μm was used as a non-conductive polymer substrate. On both sides of the polyimide film substrate 1, an electroless nickel plating layer (thickness: about 100 nm) (2, 2') and an electroless copper plating layer (thickness: about 100 nm) (3) by a horizontal electroless plating method, respectively , 3') were sequentially formed to prepare a flexible copper clad laminated film 10 as shown in FIG. 1 :

(electroless nickel plating solution)

· Plating solution: set so that the nickel ion concentration of _{nickel salt hydrate NiSO 4} ·6H _{2 O is about 5 g/L}

· Bath temperature: about 60 ℃

· Nickel precipitation time: about 1 minute

· pH concentration: about 7.3

(electroless copper plating solution)

Plating solution: 16.25 ml/L copper sulfate, 3.25 ml/L sulfuric acid

· Bath temperature: 34 ℃

· Copper precipitation time: about 2.5 minutes

· pH concentration: about 13.0

comparative example One: Flexible copper foil laminated film

A polyimide film (Kapton 100ENC, manufactured by TDC) having 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 was formed to a thickness of about 250 Å with a weight ratio of Ni and Cr of 80:20 (purity: 99.9% or more), and the Cu seed layer was formed to a thickness of about 1000 Å using 99.995% pure copper. A flexible copper foil laminated film was prepared by forming with:

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 an electrolytic plating method using a copper sulfate plating solution. At this time, the plating solution was performed using a solution of Cu ^{2 +} concentration of about 26 g / L and sulfuric acid of about 188 g / L. Comparative Example 1, except that a flexible copper clad laminate was prepared by applying a current at a bath temperature of about 30 ° C. with a current density of about 1.7 A/dm ^{2 to form a copper electrolytic plating layer having a thickness of about 4 μm.} A flexible copper clad laminated film was manufactured in the same manner as described above.

Analysis example 1: XRD analysis

An XRD analysis experiment was performed on each of the flexible copper foil laminated films according to Example 1, Comparative Example 1, and Comparative Example 2. For the XRD analysis, a CuK-alpha characteristic X-ray wavelength of 1.541 Å was used. In the flexible copper clad laminated film according to Example 1, as shown in FIG. 2, a peak of (111) plane was observed at a Bragg 2Θ angle of 43°. After leaving the flexible copper clad laminated films according to Example 1, Comparative Example 1, and Comparative Example 2 to stand for 60 days, the half maximum width ((FWHM) obtained from the peak of the (111) plane was used to calculate the half maximum width by Equation 1 below. The rate of change was calculated, and the results are shown in Table 1 below.

<Equation 1>

Width at half maximum (111) change rate = {(width at half maximum after leaving for 60 days) - (initial width at half maximum)}

division Initial full width at half maximum (FWHM, °) After leaving for 60 days (FWHM,°) Half width change rate (°) Example 1 0.25 0.24 0.01 Comparative Example 1 0.242 0.147 0.095 Comparative Example 2 0.101 0.077 0.024

Referring to Table 1, after standing for 60 days for the flexible copper foil laminated film according to Example 1, there was little change in the half-width variation with respect to the peak of the (111) plane to 0.01, but the flexible copper foil according to Comparative Examples 1 and 2 The laminated film showed some changes at 0.095 and 0.024.

From this, it can be seen that the crystallinity of the flexible copper clad laminated film according to Example 1 was improved compared with the flexible copper clad laminated films according to Comparative Examples 1 and 2.

Analysis example 2: Dimensional stability analysis

The dimensional stability of the polyimide base film of the flexible copper clad laminated films according to Example 1, Comparative Example 1, and Comparative Example 2 was analyzed for 60 days. The results are shown in Table 2 below.

Dimensional stability was analyzed as follows.

Samples of the flexible copper foil laminated films according to Example 1, Comparative Example 1, and Comparative Example 2 were cut to a size of 295 mm x 235 mm were prepared. Eight standard points were marked for the sample (Fig. 3(a)). The average value (initial dimension) was obtained by measuring the distance between the standard points with a three-dimensional measuring instrument (FIG. 3(b)). 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 and left in a constant temperature and humidity room for 24 hours, and then the distance between eight points corresponding to the standard point for the polyimide base film was measured with a three-dimensional measuring instrument, and the average value (1 to 60 Dimensions after standing for one day) were calculated, and the value obtained by subtracting the smallest dimension from the largest dimension among the dimensions was used as the dimensional change rate.

Example 1 Comparative Example 1 Comparative Example 2 Early 0.107 0.065 0.054 Dimensions after leaving for 5 days 0.104 0.071 0.059 Dimensions after leaving for 7 days 0.106 0.067 0.061 Dimensions after leaving for 10 days 0.096 0.068 0.055 Dimensions after leaving for 15 days 0.099 0.069 0.056 Dimensions after leaving for 20 days 0.097 0.057 0.064 Dimensions after leaving for 30 days 0.110 0.053 0.059 Dimensions after leaving for 45 days 0.098 0.056 0.047 Dimensions after leaving for 60 days 0.099 0.053 0.049

Referring to Table 2, it can be seen that the dimensional change rate of the flexible copper clad laminated film according to Example 1 with respect to the polyimide base film is 0.014. It can be seen that the rate of change is 0.018 and 0.017, respectively. From this, it can be seen that the flexible copper clad laminated film according to Example 1 has excellent dimensional stability for 60 days with respect to the polyimide base film compared to the flexible copper clad laminated films according to Comparative Examples 1 and 2.

1: Non-conductive polymer substrate (polyimide film)
2, 2': Nickel-containing plating layer (electroless nickel plating layer)
3, 3': copper plating layer (electroless copper plating layer),
10: flexible copper foil laminated film

Claims (10)

non-conductive polymeric substrates;
Electroless nickel plating layers located on both sides of the substrate;
including; an electroless copper plating layer positioned on the electroless nickel plating layer;
The electroless copper plating layer is a flexible copper clad laminated film in which the half-width variation calculated by the following Equation 1 for the peak of the (111) plane in the X-ray diffraction spectrum is 0.01° or less:
<Equation 1>
Width at half maximum (111) Change rate = {(width at half maximum after leaving for 60 days) - (initial width at half maximum)} According to claim 1,
The electroless copper plating layer was left for 60 days for the peak of the (111) plane in the X-ray diffraction spectrum, and then the half-width and the initial half-width are 0.20 to 0.35 °, respectively. delete According to claim 1,
The thickness of the electroless copper plating layer is 40 nm to 150 nm, flexible copper foil laminated film. According to claim 1,
Cut the flexible copper clad laminated film to a size of 295mm x 235mm, mark 8 dots in the cut flexible copper clad laminated film, measure the distance between the 8 dots, and take the initial dimension as 23±2 ° C. After leaving at 50±5% for 1 to 60 days, heat treatment at 150° C. for 30 minutes, leaving it for 24 hours, measuring the distance between the eight points, leaving it for 1 to 60 days, obtaining the dimensions, and measuring the initial dimensions and a dimensional change rate of 0.015 or less with respect to the substrate, which is a value obtained by subtracting the minimum dimension from the maximum dimension among the dimensions left for 1 to 60 days. delete According to claim 1,
The thickness of the electroless nickel plating layer is 40 nm to 250 nm, a flexible copper foil laminated film. According to claim 1,
The non-conductive polymer substrate comprises at least one selected from a phenol-based resin, a phenolaldehyde-based resin, an allyl-based resin, an epoxy-based resin, a polyethylene-based resin, a polypropylene-based resin, a polyester-based resin, and a polyimide-based resin , Flexible copper foil laminated film. An electronic device comprising the flexible copper foil laminated film according to any one of claims 1, 2, 4, 5, 7, and 8. preparing a non-conductive polymer substrate;
forming a nickel-containing electroless plating layer on both surfaces of the substrate; and
A copper electroless plating layer is formed on one surface of the nickel-containing electroless plating layer to laminate the flexible copper foil according to any one of claims 1, 2, 4, 5, 7, and 8. Manufacturing method of a flexible copper foil laminated film comprising; manufacturing a film.

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