JP2023000377A - Laminate, and copper-clad laminate - Google Patents

Abstract

To provide a copper-clad laminate (CCL) that comprises polyether ether ketone (PEEK) resin as a substrate film, the copper-clad laminate (CCL) capable of reducing energy when heat-laminating the PEEK resin and a copper foil, having close adhesion between the PEEK resin and the copper foil, also having high dimensional stability, and exhibiting high solder heat resistance; and to provide a laminate containing a substrate film of a PEEK resin that can be used to make the copper-clad laminate (CCL), in order to obtain the copper-clad laminate (CCL).SOLUTION: A laminate has a coating layer containing powder composed of a high-melting-point adhesive resin, the coating layer laminated on at least one side of a substrate film composed of a polyether ether ketone (PEEK) resin.SELECTED DRAWING: None

Description

The present invention relates to laminates and copper-clad laminates.

In recent years, with the increase in communication speed and capacity in communication devices such as smartphones, the circuit boards used in these communication devices are required to have lower electrical signal loss, finer pitch circuit patterns, and higher precision. Therefore, fine circuit formation is demanded.
A copper clad laminate (CCL), which is the main material of a circuit board, a copper clad laminate (CCL) in which a copper foil is laminated on the surface of a base film made of an insulating resin, is also required to have the same performance as the above circuit board. .
Various improved copper clad laminates (CCL) have been proposed (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2011-14801

By the way, for the full-scale introduction of next-generation mobile communication systems such as 5G, it is desired to provide a copper-clad laminate (CCL) using a low-dielectric substrate (base film).
Copper-clad laminates (CCLs) using substrates of liquid crystal polymer (LCP) resin or modified polyimide (MPI) resin have been studied as low dielectric material substrates from the polyimide resin substrate described in Patent Document 1.
However, the liquid crystal polymer (LCP) resin has a problem in that it is difficult to form a film because of its poor film-forming properties, and the modified polyimide (MPI) resin has a problem in that it is highly hygroscopic and its dielectric constant changes with moisture.

Therefore, there is a movement to use a polyetheretherketone (PEEK) resin substrate (base film) as a low dielectric material substrate.
However, since the PEEK resin has a high melting point, a high energy is required, for example, to laminate a PEEK resin base film and a copper foil together for thermal lamination. In addition, when heated at a high temperature, the PEEK resin shrinks, which changes the dimensions of the base film and deteriorates the dimensional stability of the copper clad laminate (CCL).
On the other hand, if a material with a too low melting point is used as the base film of the copper clad laminate (CCL), for example, when a soldering heat resistance test is conducted to evaluate the effects of thermal stress on electronic components during the mounting process, the solder The resulting copper clad laminate (CCL) lacks heat resistance.

Therefore, the present invention provides a copper-clad laminate (CCL) using a polyetheretherketone (PEEK) resin as a base film, in which the energy required for thermal lamination of the PEEK resin and the copper foil can be reduced, and the PEEK resin is It is an object of the present invention to provide a copper clad laminate (CCL) which has excellent adhesion between a copper foil and a copper foil, has excellent dimensional stability, and exhibits good solder heat resistance. Another object of the present invention is to provide a laminate containing a PEEK resin base film that can be used to produce the copper clad laminate (CCL), in order to obtain the copper clad laminate (CCL).

As a result of intensive studies to solve the above problems, the present inventors have found that a coating film containing a specific adhesive resin powder is disposed between a PEEK resin base film and a copper foil. The inventors have found that a tension laminate (CCL) can solve the above problems, and have completed the present invention.

The present invention includes the following aspects.
[1] A laminate in which a coating film containing a powder of a high-melting adhesive resin is laminated on at least one surface of a base film made of a polyetheretherketone (PEEK) resin.
[2] The laminate according to [1], wherein the powder made of the adhesive resin having a high melting point has a melting point higher than 180°C and lower than 345°C.
[3] The high-melting adhesive resin is polyetherketoneketone (PEKK) resin, polyamideimide (PAI) resin, polyphenylene sulfide (PPS) resin, polyethersulfone (PES) resin, polysulfone (PSU) resin, poly Tetrafluoroethylene (PTFE) resin, tetrafluoroethylene perfluoroalkyl (PFA) resin, thermoplastic polyimide (TPI) resin, polyetherimide (PEI) resin, polyarylate resin (PAR), and at least selected from these resins The laminate according to any one of [1] to [2], which is at least one kind selected from alloy resins consisting of two or more kinds.
[4] The laminate according to any one of [1] to [3], wherein the powder made of the adhesive resin having a high melting point has an average particle size of 0.1 to 50 μm.
[5] The laminate according to any one of [1] to [4], wherein the coating film further contains an inorganic filler.
[6] The laminate according to any one of [1] to [5], wherein the coating film has a thickness of 1 to 50 μm and the base film has a thickness of 5 to 250 μm.
[7] A copper clad laminate (CCL), which is obtained by laminating a copper foil on the coating film of the laminate according to any one of [1] to [6].
[8] The copper clad laminate (CCL) according to [7], wherein the copper clad laminate (CCL) has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.003 or less.
[9] The copper clad laminate (CCL) according to [7] or [8], wherein the copper foil in contact with the coating film has a surface roughness (Rz) of 5 µm or less.
[10] A step of applying a paint containing a powder made of a high-melting adhesive resin on at least one surface of a base film made of a polyetheretherketone (PEEK) resin to form a coating film;
a step of drying the coating film;
placing a copper foil on the dried coating film and thermocompression bonding the base film and the copper foil film together via the coating film; Production method.
[11] The copper-clad laminate (CCL) according to [10], wherein the thermocompression bonding temperature is higher than the melting point of the powder made of the high-melting adhesive resin and lower than the melting point of the polyetheretherketone (PEEK) resin. ) manufacturing method.

According to the present invention, in a copper clad laminate (CCL) using a polyether ether ketone (PEEK) resin as a base film, the energy required for thermal lamination of the PEEK resin and the copper foil can be reduced, and the PEEK resin can be It is possible to provide a copper-clad laminate (CCL) that exhibits excellent adhesion between a copper foil and a copper foil, excellent dimensional stability, and excellent soldering heat resistance. Moreover, in order to obtain the copper clad laminate (CCL), it is possible to provide a laminate containing a base film of PEEK resin that can be used for producing the copper clad laminate (CCL).

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of a structure of the copper clad laminated board of this invention. FIG. 3 is a cross-sectional view showing another example of the configuration of the copper-clad laminate of the present invention;

Hereinafter, the copper-clad laminate of the present invention and the laminate that can be used to produce the copper-clad laminate will be described in detail. is an example and is not specific to these contents.
The following term definitions apply throughout the specification and claims.
The melting point in the present invention means the peak top temperature of the endothermic peak when the temperature is raised from room temperature at a rate of 10° C./min in a differential scanning calorimeter (DSC). When no endothermic peak occurs, the temperature at the inflection point is taken as the melting point.
The film thickness of the substrate film, coating film, copper foil (also referred to as copper foil film), etc. is the average value obtained by observing the cross section of the measurement target using a microscope, measuring the thickness at five locations, and averaging the thickness.

(Laminate)
The laminate of the present invention can be used to make copper clad laminates (CCL).
The laminate of the present invention is obtained by laminating a coating film containing a powder made of a high-melting adhesive resin on at least one surface of a base film made of a PEEK resin.
In the laminate of the present invention, coating films may be laminated on both sides of the base film.

<Base film>
In the present invention, a polyetheretherketone (PEEK) film is used as the base film.
The base film can contain a filler.

<<Filler>>
The base film can contain a filler in order to provide various functions such as strength, insulation, heat resistance, and adjustment of the coefficient of thermal expansion (CTE) of the base. Examples of fillers include inorganic fillers and organic fillers, which can be used alone or in combination.

Examples of inorganic fillers include mica, talc, boron nitride, magnesium oxide, silica, diatomaceous earth, titanium oxide, and zinc oxide. Among them, inorganic fillers such as mica, talc, boron nitride, magnesium oxide and silica are preferred.

Examples of organic fillers include, but are not limited to, organic particles of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyamide, polycarbonate, polyimide, polyetherketone, polyetheretherketone, and polymethylmethacrylate.

One of the inorganic fillers and organic fillers may be selected from the above and used alone, or two or more thereof may be used in combination. When two or more types are combined, a combination of an inorganic filler and an organic filler may be used.

The shape of the filler is not particularly limited and can be appropriately selected depending on the purpose. For example, the inorganic filler may be a spherical inorganic filler or a non-spherical inorganic filler, but a non-spherical inorganic filler is preferable from the viewpoint of coefficient of thermal expansion (CTE) and film strength. The shape of the non-spherical inorganic filler may be any three-dimensional shape other than a spherical shape (substantially spherical shape), and examples thereof include plate-like, scale-like, columnar, chain-like, and fibrous shapes. Among them, from the viewpoint of coefficient of thermal expansion (CTE) and film strength, plate-like and scale-like inorganic fillers are preferable, and plate-like inorganic fillers are more preferable.
In the case of a plate-like or scale-like inorganic filler, the average particle size in the plane direction is 0.05 μm or more and 20 μm or less, preferably 0.1 μm or more and 15 μm or less, preferably 0.1 μm or more and 10 μm or less, more preferably 0.1 μm or more. It is preferably 7 μm or less, and the aspect ratio (average major axis length/average minor axis length), which means the plane direction and thickness, is 5 or more and 500 or less from the viewpoint of coefficient of thermal expansion (CTE) and film strength. , preferably 20 or more and 500 or less, desirably 40 or more and 500 or less.
If the average particle size of the filler is 20 µm or less, the surface roughness of the substrate film can be reduced, and a smooth coating film can be easily formed.
If the aspect ratio is 5 or more, it is easy to make the CTE sufficiently small.
The larger the aspect ratio, the easier it is to adjust the CTE.

[Measurement of average particle size and aspect ratio]
The average particle size and aspect ratio of the inorganic filler can be obtained by observing, for example, using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and averaging measured values at three or more locations. Regarding the average particle size and aspect ratio of the inorganic filler present in the film (layer), for example, after embedding the film in epoxy resin, ion milling of the cross section of the film is performed using an ion milling device for cross-sectional observation. A sample is prepared, a cross section of the obtained sample is observed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the average of measured values at three or more points can be obtained.
In addition, the average particle size of the organic filler is obtained by observing the cut surface of the base film with an electron microscope and measuring the maximum diameter of at least 10 particles. It can be obtained as the average dispersed particle diameter when dispersed in the inside.

The filler content in the base film is preferably 1% by volume or more and 30% by volume or less, more preferably 3% by volume or more and 25% by volume or less.

<<Other Ingredients>>
In the present invention, the base film may optionally contain known additives as necessary. Examples of additives include antioxidants, light stabilizers, ultraviolet absorbers, crystal nucleating agents, plasticizers, filler dispersants, and the like.

<<Characteristics of base film>>
The film thickness of the substrate film is not particularly limited and can be appropriately selected depending on the intended purpose.

The surface roughness (Rz) of the base film is not particularly limited and can be appropriately selected according to the purpose. Considering various conditions, the surface roughness (Rz) of the base film is 1 μm or more. On the other hand, in order to keep the surface roughness (Rz) of the coating film formed on the base film within a desired range, the surface roughness (Rz) of the base film is preferably 10 μm or less. That is, the surface roughness (Rz) of the substrate film is preferably 1 μm or more and 10 μm or less.
As used herein, the surface roughness (Rz) refers to the ten-point average roughness of the film surface. The ten-point average roughness Rz can be obtained based on JIS B 0601:2013 (ISO 4287:1997 Amd.1:2009).

[Measurement of ten-point average roughness Rz]
The ten-point average roughness Rz (μm) of the surface of the sheet is obtained by measuring the roughness curve of the test piece using a laser microscope, and from this roughness curve, JIS B 0601: 2013 (ISO 4287: 1997 Amd.1: 2009), 10 samples are measured and the average value is obtained.

The coefficient of thermal expansion (CTE) of the base film is not particularly limited, and can be appropriately selected according to the purpose. For that reason, it is preferably 50 ppm or less, for example.
The coefficient of thermal expansion was measured in a tensile mode using a thermomechanical analyzer (product name: SII//SS7100 manufactured by Hitachi High-Tech Science) under a load of 50 mN and a temperature increase rate of 5°C/min. The temperature is increased from 25°C to 250°C at a rate of 5°C/min, the temperature change in dimensions is measured, and the coefficient of linear expansion is obtained from the slope in the range from 25°C to 125°C. ,It can be carried out.

The surface of the substrate film may be surface-treated by corona treatment, plasma treatment, or ultraviolet treatment for the reason of improving adhesion to the coating film.

<Coating film>
The coating film used in the present invention contains a powder of adhesive resin having a high melting point.
A coating film is formed by applying a paint containing the powder. The paint may contain a solvent in addition to the powder.
The coating film may contain a filler, for example, as a preferred embodiment, the coating film can contain an inorganic filler.

<<powder>>
The powder used in the present invention consists of a high-melting adhesive resin. Here, the powder can be formed using one type or two or more types of adhesive resins.
The melting point of the powder is preferably lower than the melting point of the PEEK resin. On the other hand, in order to show good results in the solder heat resistance test, the melting point of the powder is preferably higher than the temperature of the solder bath required in the solder heat resistance test.
More specifically, the melting point of the powder is preferably higher than 180°C and lower than 345°C, more preferably higher than 185°C and lower than 345°C, even more preferably higher than 278°C and lower than 330°C. C. and below 330.degree. C. are particularly preferred.

The high-melting adhesive resin used in the present invention includes polyetherketoneketone (PEKK) resin, polyamideimide (PAI) resin, polyphenylene sulfide (PPS) resin, polyethersulfone (PES) resin, and polysulfone (PSU) resin. , polytetrafluoroethylene (PTFE) resin, tetrafluoroethylene perfluoroalkyl (PFA) resin, thermoplastic polyimide (TPI) resin, polyetherimide (PEI) resin, polyarylate resin (PAR), and these resins and alloy resins composed of at least two or more of the above. By using these, the melting point of the powder can exhibit the above preferable range.

Since the high-melting-point adhesive resin used in the present invention is difficult to dissolve in solvents, in the present invention, the high-melting-point adhesive resin is pulverized and powdered to be included in the paint, so that the paint can be used as a base. It can be applied well on the material film.
The average particle size of the powder is preferably 0.1 to 50 μm, and more preferably 0.1 to 20 μm from the viewpoint of forming a uniform coating film.

[Measurement of average particle size]
The average particle size of the powder can be obtained by observing, for example, using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and averaging measured values at three or more locations. For the average particle size of the powder present in the coating film, for example, a cut surface of the coating film is observed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and at least 10 particles The average value when the maximum diameter is measured can be obtained as the average dispersed particle diameter when dispersed in the coating film by melt-kneading and dispersion.

<<Solvent>>
Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and mesitylene; methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, esters such as 3-methoxybutyl acetate; aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane; These solvents may be used alone or in combination of two or more.

<<Inorganic filler>>
The coating film may contain a filler, particularly an inorganic filler, for improving heat resistance and controlling fluidity.
The type of filler that can be contained is not particularly limited, and can be appropriately selected according to the purpose. of filler can be used.
The average particle diameter of the filler contained in the coating film is preferably 0.01 μm to 20 μm, more preferably 0.01 μm to 10 μm, and even more preferably 0.01 to 5 μm.

The content of the filler in the coating film is preferably 0.1% by volume or more and 25% by volume or less, more preferably 1% by volume or more and 20% by volume or less.
Since the coating film is required to have a higher surface smoothness than the base film, it is preferable that the average particle diameter of the filler used is smaller than that of the base film and the content thereof is small.

The thickness of the coating film can be obtained, for example, by measuring the film thickness after the production of the copper-clad laminate. Specifically, the thickness of the coating film is calculated by subtracting the thickness of the copper foil film and the substrate film from the thickness of the copper-clad laminate.
The thickness of the coating film is not particularly limited and can be appropriately selected depending on the intended purpose.

The dielectric constant and dielectric loss tangent of the laminate in the copper clad laminate (CCL) are not particularly limited and can be appropriately selected according to the purpose. Preferably, the modulus is 3.0 or less and the dielectric loss tangent is 0.003 or less.

[Relative permittivity and dielectric loss tangent]
The dielectric constant and dielectric loss tangent were measured by the open resonator method using a network analyzer MS46122B (manufactured by Anritsu) and an open resonator Fabry-Perot DPS-03 (manufactured by KEYCOM) at a temperature of 23° C. and a frequency of 28 GHz. conditions can be measured.

In the present invention, a high-melting adhesive resin powder having a lower melting point than PEEK resin, excellent adhesion to PEEK resin, and excellent heat resistance is used, and a paint containing the powder is used as a base material of PEEK resin. It is characterized in that it is applied on a film to form a coating film. In the present invention, the high-melting-point adhesive resin is made into fine particles so that it can be easily melted and easily applied onto the substrate film. When trying to form a copper clad laminate (CCL) by laminating a copper foil film on the coating film using the laminate of the present invention, it is possible to reduce the energy required for thermal lamination of the PEEK resin and the copper foil. can. In addition, since the lamination can be performed at a temperature lower than the melting point of the PEEK resin, the dimensional variation of the PEEK resin does not occur, and a copper clad laminate (CCL) excellent in dimensional stability can be obtained. In addition, since the base film and the copper foil are bonded using a coating film containing an adhesive resin powder with a high melting point and excellent heat resistance, soldering to the obtained copper clad laminate (CCL) Good solder heat resistance can be shown even when a heat resistance test is performed.

(Copper clad laminate (CCL))
The copper-clad laminate of the present invention is obtained by laminating a copper foil film (copper foil film) on the coating film of the laminate of the present invention. A coating film and a copper foil film are laminated in this order on a substrate film.

FIG. 1 is a cross-sectional view showing an example of the configuration of the copper-clad laminate of the present invention.
A copper-clad laminate 1 is obtained by laminating a copper foil film 4 on a coating film 3 in a laminate comprising a substrate film 2 and a coating film 3 .
Thus, the copper-clad laminate 1 has the base film 2, the coating film 3, and the copper foil film 4, which are laminated in this order.
Further, in the copper-clad laminate of the present invention, a coating film and a copper foil film may be laminated on both sides of the substrate film.
FIG. 2 shows another example of the structure of the copper-clad laminate of the present invention.
The copper-clad laminate 1 of the present invention shown in FIG. 2 is formed by laminating a copper foil film 4a, a coating film 3a, a substrate film 2, a coating film 3b, and a copper foil film 4b in this order.

The base film and the coating film in the copper-clad laminate are as described in the <Base film> and <Coating film> sections described in the above (Laminate) section.

In addition, the relative dielectric constant and dielectric loss tangent of the laminate in the copper clad laminate are 3.0 or less and the dielectric loss tangent is 0.003 or less, as described in the section <Coating film> above. Preferably.

<Copper foil film>
The type of copper foil is not particularly limited, and for example, an electrolytic copper foil, a rolled copper foil, or the like can be used.
The surface roughness (Rz) of the copper foil in contact with the coating film is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 1.5 μm or less. When the surface roughness (Rz) of the copper foil is 5 μm or less, it is possible to ensure the transmission characteristics of electrical signals.
The method for measuring the surface roughness (Rz) is as described in the section <<characteristics of base film>> above.

The film thickness of the copper foil film is preferably 0.05 μm to 20 μm from the viewpoint of ensuring sufficient electrical signal transmission characteristics and enabling a fine pitch of the circuit pattern, and preferably 0.1 to 0.1 μm. It is more preferably 15 μm, and even more preferably 0.5 to 10 μm.

<Film thickness of copper-clad laminate>
The film thickness of the copper-clad laminate is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 10 μm or more and 300 μm or less, for example. When the film thickness of the copper clad laminate is at least the lower limit of the above range, the handleability is excellent and strength can be ensured. Moreover, when the thickness is equal to or less than the upper limit of the above range, lightness, thinness, shortness and flexibility can be imparted.

<Method for producing copper-clad laminate>
A method for producing a copper-clad laminate includes applying a paint containing a powder made of a high-melting adhesive resin to at least one surface of a base film made of a polyetheretherketone (PEEK) resin to form a coating film. a step of drying the coating film; and a step of placing a copper foil on the dried coating film and thermocompression bonding it, and bonding the base film and the copper foil film together via the coating film.
The method for manufacturing the copper-clad laminate will be described in more detail below.
A coating film is formed on the base film.
A copper foil film is attached to the surface of the coating film opposite to the base film.
A more specific method for forming the coating film is as follows.
The coating film is formed using a paint prepared by mixing powder, solvent, and optionally other ingredients such as filler. The mixing method is not particularly limited as long as the paint is uniform.
Since the paint used in the present invention is a solvent-containing solution or dispersion (resin varnish), it can be easily applied to a substrate film and formed into a coating film.
A resin varnish containing powder and a solvent is applied to the surface of the substrate film to form a resin varnish layer. The solvent is then removed from the resin varnish layer and the coating is dried. After that, a copper foil film is placed on the coating film, and the laminated body in which the substrate film, the coating film, and the copper foil film are laminated in this order is thermocompression bonded. As a result, the substrate film and the copper foil film are bonded together via the coating film.
Here, the method for applying the resin varnish is not particularly limited and can be appropriately selected depending on the purpose. A roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispensing method, and the like can be mentioned.

The temperature for thermocompression bonding is preferably higher than the melting point of the powder made of the high-melting adhesive resin and lower than the melting point of the polyetheretherketone (PEEK) resin.

When the copper clad laminate of the present invention is a copper clad laminate in which a coating film and a copper foil film are provided on both sides of a base film as shown in FIG. 2, one surface of the base film Alternatively, a coating film and a copper foil film can be formed by the method described above, and then a coating film and a copper foil film can be formed on the other surface of the base film by the same method. Alternatively, a method may be used in which both sides of the coating are formed together on the substrate film, and then both sides of the copper foil film placed on the coating are also formed together.

When using a substrate film or coating film surface-treated by corona treatment, plasma treatment, ultraviolet treatment, or the like, for example, after preparing the substrate film, the surface of the prepared substrate film is A coating film may be formed on the surface-treated substrate film by the method described above.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these Examples. In the following, parts and % are based on mass unless otherwise specified.

(Example 1)
<Base film>
A 100 μm film of polyetheretherketone (PEEK) resin (Sepla Film, manufactured by Shin-Etsu Polymer Co., Ltd., melting point 345° C.) was used.

<Preparation of paint 1>
A pulverized product 1 (average particle diameter 10 μm) of polyether ketone ketone (PEKK) resin (KEPSTAN 6002, manufactured by ARKEMA, melting point 305° C.) was used.
The pulverized product 1 and toluene were mixed in a ratio of 100 parts by mass: 40 parts by mass to prepare a paint 1.

<Preparation of copper-clad laminate>
The surface of the PEEK base film was corona-treated. Paint 1 obtained above was applied onto the surface-treated PEEK film.
Next, the base film with the coating film was placed in an oven and heated at 120° C. for 60 minutes to dry the coating film. The film thickness of the coating film was adjusted to 15 μm after the copper-clad laminate was produced.
A film of copper foil 1 (3EC-M1S-HTE, manufactured by Mitsui Kinzoku Co., Ltd., electrolytic copper foil, thickness 12 μm, Rz 1.8 μm) is placed on the dried coating film, followed by PEEK film, coating film, and copper foil film in that order. The laminated body laminated in (1) was placed in an oven and heated at 320° C. and 4 MPa for 10 minutes with a hot press to thermally compress the laminated body.

The copper-clad laminate of Example 1 thus obtained was subjected to the following measurements and evaluations.

[Adhesion]
According to the method specified in JIS K6854-3:1999, the adhesion of the copper-clad laminate was measured by a T-peel test at a peel speed of 300 mm/min.

[Relative permittivity and dielectric loss tangent]
The relative dielectric constant and dielectric loss tangent were measured by dissolving the copper foil laminated on the copper-clad laminate in concentrated nitric acid to remove the copper foil and preparing a film as a test sample. Fabry-Perot DPS-03 (manufactured by KEYCOM) was used, and measurement was performed by the open resonator method under conditions of a temperature of 23° C. and a frequency of 28 GHz.

[Solder heat resistance test]
In the solder heat resistance test, the copper-clad laminate was cut into a 30 mm × 30 mm specimen, and the base film surface was floated in a solder bath at 288 ° C. for 10 seconds × 3 times, swelling of the copper-clad laminate, Appearance abnormality such as peeling was confirmed.
The heat resistance of the copper-clad laminate was evaluated according to the following evaluation criteria.
○ No abnormality (no dissolution).
Δ: The adhesive layer was not peeled off, but the adhesive layer was softened and a “stain pattern” was formed.
x: Peeled off.

[Dimensional stability]
Dimensional stability was measured by measuring the dimensions before and after heating under the conditions of 150° C. for 30 minutes by preparing a film as a test piece by dissolving the copper foil laminated on the copper-clad laminate with concentrated nitric acid to remove the copper foil. .
Specifically, first, the length of the film before heating is measured, the film is placed on a stainless steel plate, treated in a hot air circulating constant temperature bath for a specified time and temperature, and then cooled to room temperature. , the length of the film was measured on the same section as previously measured.
The dimensional stability was determined by the following formula (2), and less than 0.2% was evaluated as ◯, and 0.2% or more as x.
Dimensional change rate (%) = 100 x (Lo-L)/Lo (2)
In formula (2), Lo: film length before test, L: film length after test.

The results of the above measurements and evaluations for the copper-clad laminate of Example 1 are shown in Table 1 below.

(Example 2)
In Example 1, the average particle size of the pulverized polyether ketone ketone resin 1 was changed to 5 μm, the film thickness of the coating film was changed to 10 μm, and the type of copper foil was changed to copper foil 2 (HS1-VSP, Mitsui Kinzoku A copper-clad laminate was produced in the same manner as in Example 1, except that the foil was changed to an electrolytic copper foil (thickness: 18 μm, Rz: 1.2 μm, manufactured by Co., Ltd.).

(Example 3)
In Example 1, the average particle size of the pulverized product 1 of the polyether ketone ketone resin was changed to 15 μm, and the paint contained an inorganic filler (synthetic mica, MS-100DS), and the pulverized product in the paint: inorganic filler: toluene The ratio was 100 parts by mass: 10 parts by mass: 50 parts by mass, the film thickness of the coating film was changed to 20 µm, and the type of copper foil was copper foil 2 (HS1-VSP, manufactured by Mitsui Kinzoku Co., Ltd., electrolytic copper foil, thickness A copper-clad laminate was produced in the same manner as in Example 1, except that the thickness was changed to 18 μm, Rz 1.2 μm.

(Example 4)
In Example 1, the average particle size of the pulverized polyether ketone ketone resin 1 was changed to 15 μm, the paint contained an inorganic filler (synthetic mica, MS-100DS), and the paint was polytetrafluoroethylene (PTFE) resin. (Flon (registered trademark) PTFE L173JE, AGC Co., Ltd., melting point 330 ° C.) pulverized product 2 (average particle size 10 μm) is included, and the ratio of pulverized product 1: inorganic filler: pulverized product 2: toluene in the paint is 100 mass Parts: 10 parts by mass: 10 parts by mass: 50 parts by mass, the film thickness of the coating film was changed to 20 μm, and the type of copper foil was copper foil 2 (HS1-VSP, manufactured by Mitsui Kinzoku Co., Ltd., electrolytic copper foil, thickness A copper-clad laminate was produced in the same manner as in Example 1, except that the thickness was changed to 18 μm, Rz 1.2 μm.

(Example 5)
In Example 1, the pulverized polyether ketone ketone resin 1 was an alloy (PEEK: PFA = 9: 1) resin (manufactured by Shin-Etsu Polymer Co., Ltd.) of polyether ketone ketone resin and tetrafluoroethylene perfluoroalkyl (PFA) resin. , melting point 304 ° C.) was changed to pulverized product 2 (average particle size 15 μm), the thickness of the coating film was changed to 10 μm, and the type of copper foil was changed to copper foil 2 (HS1-VSP, manufactured by Mitsui Kinzoku Co., Ltd., electrolytic copper A copper-clad laminate was produced in the same manner as in Example 1, except that the foil was changed to 18 μm thick and 1.2 μm Rz.

(Example 6)
In Example 1, the pulverized product 1 of polyether ketone ketone resin was added to the pulverized product 3 of thermoplastic polyimide (TPI) resin (Surprim TO65, manufactured by Mitsubishi Gas Chemical Co., Ltd., melting point 323 ° C.) (with an average particle size of 15 μm). Changed the thickness of the coating film to 10 μm, changed the type of copper foil to copper foil 2 (HS1-VSP, Mitsui Kinzoku Co., electrolytic copper foil, thickness 18 μm, Rz 1.2 μm), PEEK film , the coating film, and the copper foil film in this order were placed in an oven and heated at 330 ° C., 4 MPa, for 10 minutes with a heat press, and the laminate was thermocompression bonded. A copper-clad laminate was produced in the same manner.

The same measurements and evaluations as in Example 1 were performed on the copper-clad laminates produced in Examples 2 to 6.
The results of the above measurements and evaluations for the copper-clad laminates of Examples 2 to 6 are shown in Table 1 below.

(Comparative example 1)
A PEEK film similar to that of Example 1 was corona-treated on the surface of the PEEK film.
A copper foil 1 similar to that of Example 1 was placed on the surface-treated PEEK film, and the laminate of the PEEK film and the copper foil film was placed in an oven and pressed with a heat press at 360° C., 4 MPa, After heating for 10 minutes, the laminate was thermocompression bonded to produce a copper-clad laminate.

(Comparative example 2)
A copper-clad laminate was produced in the same manner as in Comparative Example 1, except that the temperature for thermocompression bonding was changed to 320° C., which is the same as in Example 1.

The copper-clad laminates of Comparative Examples 1 and 2 thus obtained were subjected to the same measurements and evaluations as in Example 1.
Table 1 below shows the results of the above measurements and evaluations for the copper-clad laminates of Comparative Examples 1 and 2.
It should be noted that the characteristics of the copper-clad laminate of Comparative Example 2 could not be evaluated because the PEEK film and the film of the copper foil 1 did not bond in the first place.

実施例で作製された本発明の銅張積層板は、ＰＥＥＫ樹脂と銅箔とを熱ラミネートする際のエネルギーを低減し、かつＰＥＥＫ樹脂と銅箔との良好な密着性を示すものであった。また、実施例で作製された本発明の銅張積層板は、寸法安定性に優れ、かつ良好なはんだ耐熱性を示すものであった。

The copper-clad laminates of the present invention produced in Examples reduced the energy required for thermal lamination of the PEEK resin and the copper foil, and exhibited good adhesion between the PEEK resin and the copper foil. . Moreover, the copper-clad laminates of the present invention produced in Examples exhibited excellent dimensional stability and good solder heat resistance.

The copper-clad laminate of the present invention can be suitably used for manufacturing FPC-related products for electronic equipment such as smart phones, mobile phones, optical modules, digital cameras, game machines, laptop computers, and medical equipment.

1 Copper clad laminate 2 Base film 3, 3a, 3b Coating film 4, 4a, 4b Copper foil film

Claims (10)

A laminate comprising a base film made of polyetheretherketone (PEEK) resin, and a coating film containing powder made of a high-melting adhesive resin laminated on at least one surface of the base film. 2. The laminate according to claim 1, wherein the powder comprising the high-melting-point adhesive resin has a melting point higher than 180[deg.]C and lower than 345[deg.]C. The high melting point adhesive resin is polyether ketone ketone (PEKK) resin, polyamideimide (PAI) resin, polyphenylene sulfide (PPS) resin, polyether sulfone (PES) resin, polysulfone (PSU) resin, polytetrafluoroethylene. (PTFE) resin, tetrafluoroethylene perfluoroalkyl (PFA) resin, thermoplastic polyimide (TPI) resin, polyetherimide (PEI) resin, polyarylate resin (PAR), and at least two or more selected from these resins The laminate according to claim 1 or 2, which is at least one selected from alloy resins consisting of: 4. The laminate according to any one of claims 1 to 3, wherein the powder made of the adhesive resin having a high melting point has an average particle size of 0.1 to 50 µm. The laminate according to any one of claims 1 to 4, wherein the coating film has a thickness of 1 to 50 µm, and the base film has a thickness of 5 to 250 µm. A copper clad laminate (CCL), which is obtained by laminating a copper foil on the coating film of the laminate according to any one of claims 1 to 5. 7. The copper clad laminate (CCL) according to claim 6, wherein the laminate in the copper clad laminate (CCL) has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.003 or less. 8. The copper clad laminate (CCL) according to claim 6 or 7, wherein the copper foil in contact with the coating film has a surface roughness (Rz) of 5 [mu]m or less. A step of applying a paint containing a powder made of an adhesive resin with a high melting point onto at least one surface of a base film made of a polyetheretherketone (PEEK) resin to form a coating film;
a step of drying the coating film;
placing a copper foil on the dried coating film and thermocompression bonding the base film and the copper foil film together via the coating film; Production method. The copper clad laminate according to claim 9, wherein the thermocompression bonding temperature in the thermocompression bonding step is higher than the melting point of the powder made of the high-melting adhesive resin and lower than the melting point of the polyetheretherketone (PEEK) resin ( CCL) manufacturing method.

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