JP7211049B2 - Composite laminate - Google Patents

Description

The present invention relates to composite laminates.

A laminate having a metal foil and an insulating layer is used as a printed wiring board by etching the metal foil.
In order to stably mount an electronic component on a printed wiring board, it is important to suppress warpage of the printed wiring board that occurs during mounting. Dimensional stability of the laminate is important for suppressing warpage of the printed wiring board.
Glass is an example of an insulating layer material having excellent dimensional stability. However, when the glass base material and the metal foil are directly bonded, metal sputtering or plating is required, which is costly and time consuming. As a method for easily laminating a glass substrate and a metal foil, there is a method of laminating via an adhesive layer. For example, a laminate of a glass film and a copper-clad laminate made of epoxy resin and copper foil has been proposed (Patent Document 1).
However, the laminate described in Patent Document 1 has insufficient electrical properties, and a semiconductor package or printed wiring board using the laminate cannot sufficiently cope with frequencies in the high frequency band.

Also, a fluoropolymer having excellent electrical properties such as a small dielectric constant and a small dielectric loss tangent is used as an insulating layer and laminated with a copper-clad laminate made of copper foil (Patent Document 2).
However, in the laminate described in Patent Document 2, a polyimide layer thicker than the fluoropolymer layer is laminated with the fluoropolymer layer in order to improve the dimensional stability by matching the linear expansion coefficients of the resin layer and the glass substrate. . Since polyimide, which has a large dielectric constant and dielectric loss tangent, occupies most of the resin layer, the electrical properties are poor.

Japanese Patent Publication No. 2004-512667 JP 2011-011457 A

If a glass substrate with a small dielectric loss tangent is used as the insulating layer, excellent electrical properties can be obtained without the resin layer. Glass with a small dielectric loss tangent includes quartz glass, etc. However, glass with a small dielectric loss tangent is generally very expensive, limiting the situations in which it can be used, and also presents manufacturing problems such as the difficulty of manufacturing large substrates. There is also
Even if a glass substrate whose dielectric loss tangent is not so small is used, the electrical properties can be improved by providing a thick fluoropolymer layer on the glass substrate. However, due to the difference in coefficient of linear expansion between the glass substrate and the metal layer, separation is likely to occur not only at the interface between the glass substrate and the fluoropolymer layer but also at the interface between the fluoropolymer layer and the metal layer. In addition, if the fluoropolymer layer is made thinner with an emphasis on dimensional stability, the effect of improving electrical properties is limited.
That is, the inventors of the present invention have found that in order to obtain the dielectric properties that are truly required for the laminate supporting the printed wiring, it is not enough to select a material having excellent dielectric properties as the material to be used. , found that it is not necessary to adjust the thickness of the material used.

The present invention provides a composite laminate having excellent dimensional stability and excellent electrical properties by using a glass substrate and a resin layer containing a tetrafluoroethylene-based polymer as insulating layers.

The present invention has the following aspects.
[1] A glass/resin laminate including a glass substrate and a resin layer in contact with at least one surface of the glass substrate; and a metal layer in contact with the resin layer of the glass/resin laminate. The composite laminate having an arithmetic mean roughness Ra of the surface of the glass substrate that is in contact with the resin layer is 1.0 μm or less, the resin layer contains a tetrafluoroethylene-based polymer, and the thickness of the glass substrate thickness is 50 to 5000 μm, the resin layer has a thickness of 1 to 100 μm, and the metal layer has a thickness of 1 to 40 μm.
[2] The dielectric property L of the glass/resin laminate obtained by the following formula (1) and provided with resin layers in contact with both surfaces of the glass substrate is 0.001 to 0.020, [1] The composite laminate according to .
Dielectric property L=(tan δ1×t1+8×tan δ2×t21)/(t1+4×t21) Equation (1)
(In the formula, tan δ1 is the dielectric loss tangent of the glass constituting the glass substrate at 28 GHz, t1 is the thickness [μm] of the glass substrate, tan δ2 is the dielectric loss tangent of the resin constituting the resin layer at 28 GHz, and t21 is the dielectric loss tangent of the glass substrate. It is the total thickness [μm] of each resin layer in contact with both surfaces)
[3] The dielectric property L of the glass/resin laminate obtained by the following formula (2) and provided with a resin layer in contact with one side of the glass substrate is 0.001 to 0.020, [1] The composite laminate according to .
Dielectric property L=(tan δ1×t1+55×tan δ2×t22)/(t1+11×t22) Equation (2)
(In the formula, tan δ1 is the dielectric loss tangent of the glass constituting the glass substrate at 28 GHz, t1 is the thickness [μm] of the glass substrate, tan δ2 is the dielectric loss tangent of the resin constituting the resin layer at 28 GHz, and t22 is the dielectric loss tangent of the glass substrate. is the thickness [μm] of the resin layer in contact with one side)
[4] The composite laminate according to any one of [1] to [3], wherein the glass constituting the glass substrate has a dielectric loss tangent of 0.001 to 0.02 when measured at 28 GHz.
[5] The composite laminate according to any one of [1] to [4], wherein the glass substrate has a thickness of 200 to 600 μm and the resin layer has a thickness of 20 to 80 μm.
[6] The composite laminate according to any one of [1] to [5], wherein the resin layer is an extruded film of a tetrafluoroethylene polymer.
[7] The tetrafluoroethylene-based polymer of [1] to [6] has a temperature range of 260° C. or less showing a storage modulus of 0.1 to 5.0 MPa and a melting point of more than 260° C. A composite laminate according to any one of the above.
[8] The tetrafluoroethylene-based polymer has units based on tetrafluoroethylene and units based on at least one monomer selected from the group consisting of perfluoro(alkyl vinyl ether), hexafluoropropylene and fluoroalkylethylene. The composite laminate according to any one of [1] to [7].
[9] The tetrafluoroethylene-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group, [1] to [ 8] The composite laminate according to any one of the above.
[10] The composite laminate according to any one of [1] to [9], wherein the metal layer has a maximum height roughness Rz of 7.0 μm or less on the side in contact with the resin layer.
[11] According to [1] to [10], the interface between the glass substrate and the resin layer has a peel strength of 5 N/cm or more, and the resin layer has a dielectric constant of 2.0 to 3.5. A composite laminate according to any one of the above.
[12] The composite laminate according to any one of [1] to [11], wherein the metal layer is patterned.
[13] The composite laminate according to [12], which is an antenna.
[14] The composite laminate according to [12], which is a semiconductor package substrate.

The composite laminate of the present invention has excellent dimensional stability and excellent electrical properties. In addition, the composite laminate of the present invention can be easily manufactured and has excellent electrical properties without using very expensive glass.

1 is a cross-sectional view showing an example of a composite laminate in the present invention; FIG. FIG. 4 is a schematic cross-sectional view of a microstripline used for transmission loss measurement; FIG. 4 is a schematic cross-sectional view of a coplanar waveguide used for transmission loss measurement.

The following term definitions apply throughout the specification and claims.
"Arithmetic mean roughness Ra" is measured based on JIS B 0601:2013 (corresponding international standard ISO 4287:1997, Amd.1:2009). The reference length lr (cutoff value λc) for the roughness curve when obtaining the arithmetic mean roughness Ra is set to 0.8 mm.
"Ra (laser microscope)" is the arithmetic mean roughness Ra when measured with a laser microscope. Ra (laser microscope) is a value measured using a laser microscope "VK-X" manufactured by Keyence Corporation.
“tan δ1” and “tan δ2” are dielectric loss tangent values measured at 25° C. and 28 GHz using a cavity resonator and a vector network analyzer according to the method specified in JIS R 1641:2007.
The "maximum height roughness Rz" is measured based on JIS B 0601:2013 (corresponding international standard ISO 4287:1997, Amd.1:2009), like the arithmetic mean roughness Ra.
"Relative permittivity" is measured according to the transformer bridge method in accordance with ASTM D150 in a test environment where the temperature is kept within the range of 23°C ± 2°C and the relative humidity is kept within the range of 50% ± 5% RH. It is a value obtained at 1 MHz using a destructive testing device.

The composite laminate of the present invention is obtained by directly laminating a resin layer (hereinafter also referred to as "F resin layer") containing a tetrafluoroethylene polymer (hereinafter also referred to as "TFE polymer") on the surface of a glass substrate. It is a laminate in which a metal layer is directly laminated on the F resin layer of the glass/resin laminate.
Examples of the layer structure of the composite laminate of the present invention include glass substrate/F resin layer/metal layer, F resin layer/glass substrate/F resin layer/metal layer, and metal layer/F resin layer/glass substrate/F resin. layer/metal layer. "Glass substrate/F resin layer/metal layer" indicates that a glass substrate, an F resin layer, and a gold layer are laminated in this order, and the same applies to other layer configurations.

Examples of the glass used for the glass substrate in the present invention include soda lime glass, aluminosilicate glass, borosilicate glass, and alkali-free aluminoborosilicate glass. They can be properly used according to the desired characteristics.

As the glass substrate, it is preferable to use glass having a dielectric loss tangent (hereinafter also referred to as tan δ) at 28 GHz of 0.001 to 0.02.
When low loss is desired, it is preferable to use glass having a tan δ of 0.01 or less at 28 GHz as the glass substrate. It is more preferably 0.008 or less.

By using a glass having a tan δ at 28 GHz within the above range, desired low loss at high frequencies can be obtained. As a specific glass system, alkali-free aluminoborosilicate glass is suitable. Such an alkali-free aluminoborosilicate glass includes, for example, SiO ₂ of 50 to 80%, Al ₂ O ₃ of 1 to 20%, B ₂ O ₃ of 1 to 30%, R 'O is 1 to 30% (where R' = Mg, Ca, Sr, Ba, Zn) and R"O is 0 to 0.1% or less (where R" = Li, Na, K). be done. Among such glasses, the total content of R″O is in the range of 0.001 to 5%, and the molar ratio of Na ₂ O/(Na ₂ O+K ₂ O) in the alkali metal oxides is It is preferable that the ratio is in the range of 0.01 to 0.99.In addition, the total content of Al ₂ O ₃ and B ₂ O ₃ is in the range of 1 to 40%, and Al ₂ O ₃ /AlO ₃ +B ₂ O ₃ ) is in the range of 0 to 0.45 and the content of SiO ₂ is the largest in the ratio of components in mol % based on oxides. Such a glass substrate is obtained by the method described in WO2018/051793.

The glass substrate in the present invention is an inexpensive glass whose tan δ of the glass itself is 0.01 or more. typical tan δ can be reduced. In the present invention, it is also preferable that the tan δ of the glass itself is 0.01 to 0.02. Such glass includes soda lime glass.

The thickness of the glass substrate is 50-5000 μm, preferably 100-1000 μm, more preferably 200-600 μm. When it is at least the lower limit, the glass substrate maintains flatness and is less likely to deform. A printed wiring board can be fully thinned as it is below the said upper limit.

The arithmetic mean roughness Ra of the surface of the glass substrate is 1.0 μm or less, preferably 0.5 μm or less, more preferably 0.001 to 0.1 μm. When it is at least the lower limit of the above range, the surface of the glass substrate is sufficiently roughened, and the adhesiveness between the glass substrate and the F resin layer is further excellent. When the thickness is equal to or less than the upper limit of the range, deterioration of the mechanical strength of the glass substrate can be suppressed, and deterioration of transmission loss can be suppressed.
It is also preferable to measure Ra of the surface of the glass substrate with a laser microscope. Ra (laser microscope), which is the arithmetic mean roughness Ra measured with a laser microscope, is also preferably 0.5 μm or less, more preferably 0.001 to 0.1 μm. The reason why it is preferable is the same as for the above arithmetic mean roughness Ra.

The F resin layer in the present invention contains a TFE-based polymer.
The F resin layer may contain inorganic fillers, resins other than the TFE-based polymer, additives, and the like, if necessary, as long as the effects of the present invention are not impaired.
As the TFE-based polymer constituting the F resin layer, it is preferable to use a polymer having a tan δ of 0.001 to 0.02 at 28 GHz.
The thickness of the F resin layer is 1 to 100 μm, preferably 20 to 80 μm, more preferably 50 to 80 μm. If the thickness of the F resin layer is at least the above lower limit, the transmission characteristics as a printed wiring board are further improved. When the thickness of the F resin layer is equal to or less than the upper limit, the dimensional stability of the composite laminate is excellent.

The ratio of the thickness of the F resin layer to the thickness of the glass substrate is preferably 0.01 to 0.30, particularly preferably 0.05 to 0.20. If the ratio of the thickness of the F resin layer to the thickness of the glass substrate is equal to or greater than the above lower limit, the transmission characteristics of the printed wiring board are further improved. When the ratio of the thickness of the F resin layer to the thickness of the glass substrate is equal to or less than the upper limit, the composite laminate has excellent dimensional stability.

The dielectric property L of the glass/resin laminate obtained by the formula (1) or (2) is 0.001 to 0.020, preferably 0.005 to 0.015. The dielectric property L is the electrical property of the laminate substrate supporting the printed wiring that affects the transmission performance of the printed wiring. When the dielectric property L is within this range, excellent transmission characteristics and excellent dimensional stability are achieved.

The dielectric property L defined by Equation (1) or Equation (2) correlates with the measured value of transmission loss. Specifically, when the value of the dielectric property L is small, the measured value of the transmission loss is also small, and the dielectric property is excellent.
In order to make this tendency clearer, it is also preferable to appropriately select Equation (1) or Equation (2) according to the conditions for measuring transmission loss.
For example, it is preferable to use equation (1) to approximate the trend of transmission loss measured using a microstrip line (MSL).
In addition, it is preferable to use equation (2) when the transmission loss is brought closer to the tendency when measured using a coplanar wave guide (CPW).

In formula (1), the dielectric property L is preferably 0.003 to 0.015, more preferably 0.005 to 0.010.
In formula (2), the dielectric property L is preferably 0.005 to 0.015, more preferably 0.005 to 0.010.

In the composite laminate of the present invention, materials for the metal layer include copper, copper alloys, stainless steel, nickel, nickel alloys (including 42 alloys), aluminum, aluminum alloys, titanium, titanium alloys, and the like.
The metal layer is preferably made of metal foil, and examples thereof include rolled copper foil and electrolytic copper foil. A rust-preventive layer (an oxide film such as chromate, etc.), a heat-resistant layer, or the like may be formed on the surface of the metal foil.

The thickness of the metal layer is 1-40 μm, preferably 10-30 μm.
The surface of the metal layer may be treated with a silane coupling agent, the entire surface of the metal layer may be treated with the silane coupling agent, or a portion of the surface of the metal layer may be treated with the silane coupling agent. may have been

The maximum height roughness Rz of the surface of the metal layer is preferably 7.0 μm or less, more preferably 5.0 μm or less, and even more preferably 3.0 μm or less. In this case, the adhesiveness to the F resin layer is improved, and a printed wiring board having excellent transmission characteristics can be easily obtained.

In the composite laminate of the present invention, the dielectric constant of the F resin layer is preferably 2.0 to 6.0, more preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. If the dielectric constant is equal to or less than the upper limit of the above range, the composite laminate can be suitably used for printed wiring boards and the like that require a low dielectric constant. If the dielectric constant of the F resin layer is equal to or higher than the lower limit value of the above range, the electric properties of the F resin layer are excellent.
The F resin layer is preferably a non-porous resin layer. The non-porous resin layer is excellent in electrical properties and acid resistance (etching resistance, etc.). The non-porous resin layer has substantially no voids, except for voids present at the interface with the glass substrate. As such a non-porous resin layer, which can be said to be a dense resin layer, a resin layer made of a resin melt is preferable.

The TFE-based polymer is preferably a polymer that can be melt-molded, and its melting point is preferably above 260°C, more preferably above 260°C and 320°C or less, and particularly preferably from 275 to 320°C. When the melting point of the TFE-based polymer is within the above range, the TFE-based polymer can be baked while maintaining its adhesiveness based on its elasticity, and it is easier to form a dense F resin layer.
The TFE-based polymer preferably has a temperature range of 260° C. or lower in which it exhibits a storage modulus of 0.1 to 5.0 MPa. The storage elastic modulus of the TFE-based polymer is preferably 0.2-4.4 MPa, particularly preferably 0.5-3.0 MPa. The temperature range in which the TFE-based polymer exhibits such storage elastic modulus is preferably 180 to 260°C, particularly preferably 200 to 260°C. In the above temperature range, the TFE-based polymer tends to effectively exhibit tackiness based on its elasticity.

A TFE-based polymer is a polymer having units (hereinafter also referred to as "TFE units") based on tetrafluoroethylene (hereinafter also referred to as "TFE"). The TFE-based polymer may be a homopolymer of TFE, or a copolymer of TFE and another monomer copolymerizable with TFE (hereinafter also referred to as a comonomer). The TFE-based polymer preferably has 75 to 100 mol % of TFE units and 0 to 25 mol % of comonomer-based units relative to the total units constituting the polymer.

Examples of TFE-based polymers include polytetrafluoroethylene, a copolymer of TFE and ethylene, a copolymer of TFE and propylene, a copolymer of TFE and perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), and TFE and hexafluoropropylene. (hereinafter also referred to as "HFP"), a copolymer of TFE and fluoroalkylethylene (hereinafter also referred to as "FAE"), and a copolymer of TFE and chlorotrifluoroethylene.
PAVE includes CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ =CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF2 ₌ CFO _{( CF2} )8F can be mentioned.
As FAE, _CH2 =CH(CF2) _2F , _CH2 =CH(CF2) _3F , _CH2 =CH( _CF2 ) _4F , _{CH2 =} CF _{( CF2} ) _3H , _CH2 =CF ₍ CF2) _4H .

Preferred embodiments of the TFE-based polymer also include polymers containing units based on TFE units and at least one monomer selected from the group consisting of PAVE, HFP and FAE (hereinafter also referred to as "comonomer unit F"). be done.
The polymer preferably has 90 to 99 mol % of TFE units and 1 to 10 mol % of comonomer units F relative to the total units constituting the polymer. The polymer may consist only of TFE units and comonomer units F, or may also contain other units.

A preferred embodiment of the TFE-based polymer is at least one selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, an amide group, an amino group and an isocyanate group, from the viewpoint of adhesion between the F resin layer and the glass substrate. A polymer having a TFE unit (hereinafter also referred to as "polymer F1") having one type of functional group (hereinafter also referred to as "functional group") is also included.
The functional group may be contained in a unit in the TFE-based polymer, or may be contained in the terminal group of the main chain of the polymer F1. Examples of the latter polymer include polymers having functional groups as terminal groups derived from polymerization initiators, chain transfer agents, and the like.
As the polymer F1, a polymer having a unit having a functional group and a TFE unit is preferred. The polymer F1 in this case also preferably has further units, particularly preferably comonomer units F.

The functional group is preferably a carbonyl group-containing group from the viewpoint of adhesion between the F resin layer and the glass substrate. Examples of the carbonyl group-containing group include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue (-C(O)OC(O)-), a fatty acid residue, and the like. Anhydride residues are preferred.
Units having a functional group are preferably units based on a monomer having a functional group, units based on a monomer having a carbonyl group-containing group, units based on a monomer having a hydroxy group, units based on a monomer having an epoxy group, or isocyanate groups units based on a monomer having a carbonyl group-containing group are more preferred, and units based on a monomer having a carbonyl group-containing group are particularly preferred.

As the monomer having a carbonyl group-containing group, a cyclic monomer having an acid anhydride residue, a monomer having a carboxy group, a vinyl ester or (meth)acrylate is preferred, and a cyclic monomer having an acid anhydride residue is particularly preferred.
As the cyclic monomer, itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (also known as hymic anhydride, hereinafter also referred to as “NAH”) or maleic anhydride is preferable.

As the polymer F1, a polymer containing a unit having a functional group, a TFE unit, and a PAVE unit or an HFP unit is preferable. Specific examples of such polymer F1 include polymer (X) described in WO 2018/16644.
The proportion of TFE units in the polymer F1 is preferably 90 to 99 mol % of all units constituting the polymer F1.
The proportion of PAVE units in the polymer F1 is preferably 0.5 to 9.97 mol % of the total units constituting the polymer F1.
The proportion of units having a functional group in the polymer F1 is preferably 0.01 to 3 mol % of the total units constituting the polymer F1.

The surface Ra of the F resin layer is preferably measured with an atomic force microscope (AFM). The arithmetic mean roughness Ra (AFM) measured by AFM is preferably 3.0 nm or more, more preferably 8.0 nm or more, and even more preferably 12 nm or more. When the surface Ra (AFM) of the F resin layer is at least the lower limit value of the above range, the adhesion between the F resin layer and the metal layer is excellent. Ra (AFM) is preferably 1 μm or less.
Ra (AFM) of the surface of the F resin layer is measured on the surface in the range of 1 μm ² under the following measurement conditions using an AFM manufactured by Oxford Instruments.
Probe: AC160TS-C3 (tip radius <7 nm, spring constant 26 N/m), measurement mode: AC-Air, Scan Rate: 1 Hz.

In the composite laminate of the present invention, the peel strength at the interface between the glass substrate and the F resin layer is preferably 5 N/cm or more, more preferably 10 N/cm or more.

The method for producing the composite laminate of the present invention includes a method of laminating a glass base material, a material capable of forming an F resin layer, and a material capable of forming a metal layer in this order, followed by thermocompression bonding. Materials that can form the F resin layer include a film containing a TFE polymer (hereinafter also referred to as "F resin film"). A metal foil is mentioned as a material which can form a metal layer.

The temperature during crimping is at least the melting point of the TFE polymer, preferably at least 10°C higher than the melting point, more preferably at least 20°C higher than the melting point, and even more preferably at least 40°C higher than the melting point. Preferably, the temperature during crimping does not exceed 3°C above the melting point. If the temperature during pressure bonding is within the above range, the glass substrate, the F resin layer and the metal layer can be sufficiently bonded while suppressing thermal deterioration of the TFE polymer. The temperature during crimping is the temperature of the hot platen.

The pressure during crimping is preferably 0.2 MPa or higher, more preferably 0.5 MPa or higher, and even more preferably 1.0 MPa or higher. The pressure during crimping is preferably 10.0 MPa or less. If the pressure during crimping is within the above range, the F resin layer and the metal layer can be sufficiently bonded without damaging the glass substrate. In addition, it becomes possible to fill the pores of the glass substrate with the resin.

Thermocompression bonding is preferably performed in a vacuum atmosphere. The degree of vacuum is preferably 100 kPa or less, more preferably 50 kPa or less, and even more preferably 20 kPa or less. If the degree of vacuum is within the above range, it is possible to suppress the inclusion of air bubbles in the respective interfaces of the F resin layer, the glass base material and the metal layer, which constitute the laminate, and at the same time suppress deterioration due to oxidation.
Moreover, it is preferable to raise the temperature after reaching the degree of vacuum. If the temperature is raised before the degree of vacuum is reached, the F resin layer is pressed in a softened state, that is, in a state in which it has a certain degree of fluidity and adhesion, which causes air bubbles.

The glass substrate in the present invention may be surface-treated before thermocompression bonding.
As the surface treatment of the glass substrate, wet treatment or plasma treatment is preferred, and wet treatment is particularly preferred, from the viewpoint of further improving the adhesion between the glass substrate and the F resin layer. In particular, when the glass substrate has holes, by wet-treating the surface of the glass substrate, the TFE-based polymer sufficiently penetrates into the holes, and a laminate can be produced without the TFE-based polymer missing in the holes.

The wet treatment is a treatment that brings a wet treatment liquid into contact with the surface of the glass substrate and exhibits one or more of the following effects. Effects include surface cleaning and surface modification. When holes are formed in the inorganic layer, wet treatment is preferably used because the inner wall surfaces of the holes are difficult to activate by plasma treatment or ultraviolet irradiation.

The wet treatment liquid used for surface cleaning is appropriately selected according to the object of contamination (oil, flux, abrasive, release agent, fine particles, etc.). The wet processing liquid may be an aqueous wet processing liquid or a non-aqueous wet processing liquid. The aqueous wet treatment liquid may be neutral, alkaline, or acidic. Examples of non-aqueous wet treatment liquids include hydrocarbon-based wet treatment liquids, fluorine-based wet treatment liquids, bromine-based wet treatment liquids, and alcohol-based wet treatment liquids. The wet treatment liquid may contain a surfactant or the like.

The purpose of the surface modification is to introduce a reactive functional group (silanol group, amino group, hydrocarbon group, etc.) that can chemically bond with the adhesive functional group of the F resin layer to the surface of the glass substrate during thermocompression bonding. done. The surface modification is performed by etching the surface of the glass substrate, attaching a surface treatment agent to the surface of the glass substrate, or the like. Wet treatment liquids used for surface modification include known glass etching liquids (alkali aqueous solution, hydrofluoric acid aqueous solution, etc.), liquids containing surface treatment agents (silane coupling agents, cationic polymers, chelating agents, etc.), and the like.

The etchant used for surface modification may be appropriately selected from known etchants according to the material of the glass substrate. Examples of etching solutions include solutions containing hydrofluoric acid, sulfuric acid, nitric acid, perchloric acid, etc., and solutions containing alkalis such as sodium hydroxide and potassium hydroxide. When the material of the glass substrate is glass, an alkaline aqueous solution having a pH of 11 to 14 is preferable so as not to excessively roughen the surface.
The etchant used for surface modification preferably contains a chelating agent. By including the chelating agent in the etching solution, the chelating agent is coordinated to the surface of the glass substrate after the wet treatment, and the adhesion between the glass substrate and the F resin layer is further improved. The ratio of the chelating agent in the etching liquid is preferably 0.1% by mass or more. Examples of the chelating agent used in the etching solution include alkaline chelating agents described in JP-A-2016-60862.

Silane coupling agents used for surface modification include aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylsilane, ureidosilane, and alkylsilane.
Cationic polymers used for surface modification include amine-type cationic polymers such as polyethylenimine, polyallylamine, dicyandiamide-diethylenetriamine condensate, polydiallyldimethylammonium chloride, poly(dimethylaminoethyl acrylate methyl chloride quaternary salt), poly(dimethyl quaternary ammonium type cationic polymers such as aminoethyl methacrylate methyl chloride quaternary salt), trimethylammonium alkylacrylamide polymer salt, dimethylamine epichlorohydrin condensate salt, and the like.
Chelating agents used for surface modification include gluconic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethanediphosphonic acid, nitrilotrismethylenephosphonic acid, gluconic acid, ethylenediaminetetraacetic acid, citric acid, tartaric acid, and malic acid. , succinic acid, malonic acid, oxalic acid and the like.

A film containing a TFE-based polymer can be produced by molding a resin composition containing a TFE-based polymer into a film by a known melt-molding method (extrusion molding method, etc.). The resin composition may further contain components other than the TFE-based polymer, if necessary, as long as the effects of the present invention are not impaired. Components other than the TFE-based polymer include resins other than the TFE-based polymer, inorganic fillers, rubbers, various additives, and the like.
The F resin film may be produced by a casting method using a liquid composition.

The F resin film may be subjected to surface treatment prior to thermocompression bonding. Examples of the surface treatment include wet treatment, plasma treatment (atmospheric pressure plasma treatment, vacuum plasma treatment), corona treatment, UV ozone treatment, excimer treatment, etc. Vacuum plasma treatment is particularly preferred.

Methods of vacuum plasma treatment include a high-frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate method, a remote plasma method, and an ICP type high-density plasma method. Gases used for the vacuum plasma treatment include oxygen gas, nitrogen gas, rare gases (such as argon gas), hydrogen gas, ammonia gas, etc. Rare gases and nitrogen gas are preferred. One type of gas may be used alone, or two or more types may be mixed and used. For example, argon gas may be 100% by volume, hydrogen gas/nitrogen gas may be a mixed gas of 70/30 (volume ratio), hydrogen gas/nitrogen gas/argon gas may be 35/15/50 (volume ratio). A mixed gas of
The atmosphere for vacuum plasma treatment is preferably an atmosphere with a rare gas or nitrogen gas volume fraction of 50% by volume or more, more preferably 70% by volume or more, even more preferably 90% by volume or more, and 100% by volume. atmosphere is particularly preferred. If the volume fraction of the rare gas or nitrogen gas is at least the lower limit of the above range, the surface of the F resin layer can be sufficiently roughened.
The gas flow rate, the degree of vacuum, and the treatment time in the vacuum plasma treatment are appropriately selected according to the composition of the F resin layer to be surface-treated and the structure of the vacuum plasma treatment apparatus.

The composite laminate of the present invention can be used for antennas and semiconductor packaging applications by patterning the metal layers.
Photolithography is suitable for patterning the metal layer on the surface of the composite laminate. In photography, first, a resist layer is formed on the surface to be processed. A liquid resist or a film resist can be used. In the case of a liquid resist, it is applied to the substrate surface with a uniform thickness by spin coating or the like, and then a pre-baking process is performed to evaporate the organic solvent contained in the resist. In general, most liquid resists are positive (exposed portions disappear) and film resists are negative (exposed portions remain).

Next, the resist is irradiated with light to transfer the mask pattern. Mask exposure is classified into two types: mask aligner (single exposure device) that draws the pattern on the mask all at once and projects it onto the substrate, and stepper (stepper) that projects and exposes the substrate while stepping through a reduction projection lens. segmented exposure device). Since the stepper performs reduction projection exposure, it excels in fine patterning and is suitable for forming fine circuits such as semiconductor package substrates. On the other hand, the mask aligner is not suitable for fine patterning, but is suitable for forming antennas and the like because it can pattern a large area at once.

By immersing the exposed substrate in a developer, the exposed portion of the resist is removed (positive resist) or the unexposed portion is removed (negative resist), which is post-baked.
Next, the metal layer of the resist-removed portion of the substrate on which the resist is patterned is removed by etching. There are a wet etching method in which the substrate is immersed in an etchant and a dry etching method in which the substrate is placed in an etching gas and ions are used.
After etching, the resist is removed with an organic solvent or the like to complete a desired circuit.
Although the above shows an example of a subtractive process, a modified semi-additive process (MSAP) using an ultra-thin metal foil can also be used.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.
Various measurement methods are shown below.

(Ra (laser microscope))
Ra (AFM) of the surface of the glass substrate was calculated by measuring the surface unevenness using a laser microscope "VK-X" manufactured by Keyence Corporation.
Scan Area: 1000 μm square.

(Proportion of each unit in TFE polymer)
The proportion of NAH units was determined by infrared absorption spectroscopy. The proportion of units other than NAH units was determined by melt NMR analysis and fluorine content analysis.

(Infrared absorption spectrum analysis)
A film having a thickness of 200 μm was obtained by press-molding the TFE-based polymer. The films were analyzed by infrared spectroscopy to obtain infrared absorption spectra. In the infrared absorption spectrum, the absorption peak of NAH units in the TFE-based polymer appears at 1778 cm ⁻¹ . The absorbance of this absorption peak was measured, and the proportion of NAH units in the TFE-based polymer was determined using the NAH molar extinction coefficient of 20810 mol ⁻¹ ·L·cm ⁻¹ .

(Polymer storage modulus)
Based on ISO 6721-4: 1994, using a dynamic viscoelasticity measuring device (DMS6100 manufactured by SII Nanotechnology), frequency 10 Hz, static force 0.98 N, dynamic displacement 0.035%, TFE The system polymer was heated from 20°C at a rate of 2°C/min, and the storage elastic modulus at 260°C was measured.

(melting point)
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC-7020), the melting peak of the TFE polymer was recorded when the temperature was raised at a rate of 10 ° C./min, and the temperature (° C.) corresponding to the maximum value was measured. melting point.

(MFR)
Using a melt indexer (manufactured by Technoseven Co., Ltd.), the mass (g) of the TFE polymer flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm was measured for 10 minutes at 372° C. under a load of 49 N, and the MFR was obtained.

(relative permittivity)
According to the transformer bridge method in accordance with ASTM D 150, a dielectric breakdown tester (Yamayo test YSY-243-100RHO (manufactured by Kisha Ltd.) was used to determine the dielectric constant at 1 MHz. Further, in a higher frequency band, measurement was performed at a frequency of 20 GHz under an environment of 23° C.±2° C. and 50±5% RH by the SPDR (split post dielectric resonator) method.

(Peeling test)
A rectangular test piece having a length of 100 mm and a width of 10 mm was cut from the laminate. The F resin layer and the glass substrate were peeled off to a position 50 mm from one end of the test piece in the longitudinal direction. Using a tensile tester (manufactured by Orientec Co., Ltd.) at a position 50 mm from one end in the length direction of the test piece in the center, 90 ° peeling at a tensile speed of 50 mm / min, maximum load Peel strength (N / cm ).

(Production of TFE-based polymer A)
Using TFE, NAH (manufactured by Hitachi Chemical Co., Ltd., Himic Anhydride), and PPVE (manufactured by AGC), TFE-based polymer A was produced according to the procedure described in paragraph [0123] of WO 2016/017801. The ratio of each unit in TFE-based polymer A was NAH unit/TFE unit/PPVE unit=0.1/97.9/2.0 (mol %). The TFE polymer A has a storage modulus of 1.1 MPa at 260° C., a melting point of 300° C., an MFR of 17.6 g/10 min, and a dielectric constant of 2.1 (measurement frequency: 1 MHz). The fluorine content was 75% by mass, and the content of adhesive functional groups was 1000 per 1×10 ⁶ carbon atoms in the main chain of the TFE polymer A.

(Manufacture of F resin film)
Using a 65 mm diameter single screw extruder having a coat hanger die of 750 mm width, the TFE polymer A was extruded into a film at a die temperature of 340° C. to obtain an F resin film 1 having a thickness of 50 μm.
Similarly, an F resin film 2 having a thickness of 60 μm was obtained.
Similarly, an F resin film 3 having a thickness of 62 μm was obtained.
Similarly, an F resin film 4 having a thickness of 25 μm was obtained.

(Example 1)
A soda lime glass plate (manufactured by AGC, thickness: 0.3 mm, tan δ: 0.017) was prepared as a glass substrate.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to wet treatment while applying ultrasonic vibration. After being immersed for 1 hour, the glass substrate was pulled out of the liquid. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a wet-treated glass substrate. Ra (laser microscope) of the glass substrate after the wet treatment was 0.1 μm or less.
On both sides of the wet-treated glass substrate, F resin film 1 (tan δ: 0.001) and copper foil (3EC-M2S-VLP manufactured by Mitsui Kinzoku Co., Ltd., thickness 7 μm, Rz 1.8 μm) were layered in this order. The composite laminate 1 was obtained by putting it into a vacuum press machine in this state, and performing vacuum pressure bonding under the following conditions: degree of vacuum: 10 kPa, temperature during compression: 340°C, pressure during compression: 2.0 MPa, hold: 10 minutes.
One side of the obtained laminate was subjected to resist coating, mask exposure, development, and copper etching to form a microstrip line having a length of 25 mm and a width of 0.72 mm.
Transmission loss measurement at a frequency of 28 GHz was performed using the fabricated microstrip line. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -1.44 dB.
Also, the dielectric property L obtained from the formula (1) was 0.0084.

(Example 2)
Composite laminate 2 was obtained in the same manner as in Example 1, except that F resin film 1 was changed to F resin film 2 (tan δ: 0.001).
The copper foil surface of the obtained laminate was subjected to resist coating, mask exposure, development and copper etching to form a coplanar waveguide having a length of 25 mm, a slit width of 0.1 mm and a signal line width of 1.0 mm.
A transmission loss measurement was performed at a frequency of 28 GHz using the produced coplanar waveguide. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -1.10 dB.
Also, the dielectric property L obtained from the formula (2) was 0.0875.

(Example 3)
As a glass substrate, an alkali-free glass plate (composition ratio, numerical values are mol%, SiO ₂ : 66.1, Al ₂ O ₃ : 11.3, B ₂ O ₃ : 7.8, MgO: 5.1, CaO : 4.5, SrO: 5.2, thickness: 0.3 mm, tan δ: 0.0076).
The glass substrate was wet-treated, washed and dried in the same manner as in Example 1 to obtain a wet-treated glass substrate. Ra (laser microscope) of the glass substrate after the wet treatment was 0.1 μm or less.
On both sides of the wet-treated glass substrate, F resin film 3 (tan δ: 0.001) and copper foil (3EC-M2S-VLP manufactured by Mitsui Kinzoku Co., Ltd., thickness 7 um) are stacked in this order, and placed in a vacuum press. Vacuum compression bonding was performed under the following conditions: degree of vacuum: 10 kPa, temperature during compression: 340° C., pressure during compression: 2.0 MPa, hold: 10 minutes, to obtain composite laminate 3 .
One side of the obtained laminate was subjected to resist coating, mask exposure, development, and copper etching to form a microstrip line having a length of 25 mm and a width of 0.72 mm.
Transmission loss measurement at a frequency of 28 GHz was performed using the fabricated microstrip line. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -0.85 dB.
Also, the dielectric property L obtained from the formula (1) was 0.0041.

(Example 4)
A soda lime glass plate (manufactured by AGC, thickness: 0.5 mm, tan δ: 0.017) was prepared as a glass substrate.
The glass substrate was wet-treated, washed and dried in the same manner as in Example 1 to obtain a wet-treated glass substrate. Ra (laser microscope) of the glass substrate after the wet treatment was 0.1 μm or less.
On one side of the wet-treated glass substrate, F resin film 4 (tan δ: 0.001) and copper foil (3EC-M2S-VLP manufactured by Mitsui Kinzoku Co., Ltd., thickness 7 um) are stacked in this order, and placed in a vacuum press. A composite laminate 4 was obtained by vacuum pressure bonding under conditions of degree of vacuum: 10 kPa, temperature during pressure bonding: 340° C., pressure during pressure bonding: 2.0 MPa, and hold: 10 minutes.
The copper foil surface of the obtained laminate was subjected to resist coating, mask exposure, development, and copper etching to form a slit antenna.
The gain and radiation efficiency of the fabricated slit antenna were measured at a frequency of 28 GHz. A vector network analyzer was used to measure gain and radiation efficiency.
As a result of measurement, the antenna gain was 8.9 dB and the radiation efficiency was 57.5%.

(Comparative example 1)
As a glass substrate, the same soda-lime glass plate as in Example 1 was prepared.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to cleaning treatment while applying ultrasonic vibration. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a glass substrate.
After depositing Ti and Cu by sputtering on both surfaces of the cleaned glass substrate, Cu was grown to a thickness of 7 μm by electroplating.
A resist coating, mask exposure, development, and copper etching were performed on one side of the substrate on which Cu was formed on both sides to form a microstrip line with a length of 25 mm and a width of 0.72 mm.
Transmission loss measurement at a frequency of 28 GHz was performed using the fabricated microstrip line. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -3.15 dB.

(Comparative example 2)
As a glass substrate, the same alkali-free glass plate as in Example 3 was prepared.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to cleaning treatment while applying ultrasonic vibration. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a glass substrate.
After depositing Ti and Cu by sputtering on both surfaces of the cleaned glass substrate, Cu was grown to a thickness of 7 μm by electroplating.
A resist coating, mask exposure, development, and copper etching were performed on one side of the substrate on which Cu was formed on both sides to form a microstrip line with a length of 25 mm and a width of 0.72 mm.
Transmission loss measurement at a frequency of 28 GHz was performed using the fabricated microstrip line. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -1.55 dB.

(Comparative Example 3)
As a glass substrate, the same soda-lime glass plate as in Example 1 was prepared.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to cleaning treatment while applying ultrasonic vibration. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a glass substrate.
After depositing Ti and Cu by sputtering on one side of the cleaned glass substrate, Cu was grown to a thickness of 7 μm by electroplating.
A substrate having Cu formed on one side was subjected to resist coating, mask exposure, development, and copper etching to form a coplanar waveguide having a length of 25 mm, a slit width of 0.1 mm, and a signal line width of 1.0 mm. .
A transmission loss measurement was performed at a frequency of 28 GHz using the produced coplanar waveguide. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -2.15 dB.

(Comparative Example 4)
As a glass substrate, the same alkali-free glass plate as in Example 3 was prepared.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to cleaning treatment while applying ultrasonic vibration. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a glass substrate.
After depositing Ti and Cu by sputtering on one side of the cleaned glass substrate, Cu was grown to a thickness of 7 μm by electroplating.
A substrate having Cu formed on one side was subjected to resist coating, mask exposure, development, and copper etching to form a coplanar waveguide having a length of 25 mm, a slit width of 0.1 mm, and a signal line width of 1.0 mm. .
A transmission loss measurement was performed at a frequency of 28 GHz using the produced coplanar waveguide. Anritsu Universal Test Fixture 3680 was used for transmission loss measurement.
As a result of measurement, the transmission loss was -1.08 dB.

(Comparative Example 5)
As a glass substrate, the same soda-lime glass plate as in Example 4 was prepared.
The glass substrate was immersed in a glass cleaning solution (undiluted solution of Semi-Clean GE-5 manufactured by Yokohama Yushi Kogyo Co., Ltd., pH: 13) at 23° C., and subjected to cleaning treatment while applying ultrasonic vibration. After thoroughly washing the glass substrate with pure water, it was dried by an air blow to obtain a glass substrate.
After depositing Ti and Cu by sputtering on one side of the cleaned glass substrate, Cu was grown to a thickness of 7 μm by electroplating.
A slit antenna was produced by applying a resist to the Cu surface of the substrate having Cu formed on one side thereof, exposing it to a mask, developing it, and etching it to copper. The gain and radiation efficiency of the fabricated slit antenna were measured at a frequency of 28 GHz. A vector network analyzer was used for gain and radiation efficiency measurements.
As a result of measurement, the antenna gain was 5.5 dB and the radiation efficiency was 44.0%.

A comparison between Example 1 and Comparative Example 1 shows that when the same soda-lime glass is used as the glass base material, the interposition of the F resin layer can improve the transmission loss of the MSL by 1.71 dB.
By comparing Example 1 and Comparative Example 2, even if soda lime glass, which has a lower tan δ than alkali-free glass and is inexpensive, is used, by interposing the F resin layer, the same MSL as when using alkali-free glass is obtained. It can be seen that the transmission loss at
A comparison between Example 2 and Comparative Example 3 shows that when the same soda lime glass is used as the glass base material, the transmission loss of CPW can be improved by 1.05 dB by interposing the F resin layer.
By comparing Example 2 and Comparative Example 4, even if soda-lime glass, which has a lower tan δ than alkali-free glass and is inexpensive, is used, by interposing the F resin layer, the CPW is equivalent to that when alkali-free glass is used. It can be seen that the transmission loss at
A comparison between Example 3 and Comparative Example 2 shows that when the same alkali-free glass is used, the transmission loss of MSL can be improved by 0.71 dB by interposing the F resin layer.
Comparative Examples 1 to 4 require sputtering and electrolytic plating to form a Cu layer on the glass, which is costly and time consuming. On the other hand, in Examples 1 to 3, since the copper foil is simply vacuum hot-pressed through the F resin layer, it can be processed at low cost in a short time.
By comparing Example 4 and Comparative Example 5, when a slit antenna was produced using the same soda-lime glass as the glass substrate, the interposition of the F resin layer improved the antenna gain by 3.4 dB and the radiation efficiency. It can be seen that 13.5% improvement can be achieved.

The composite laminate of the present invention is useful for antennas and semiconductor packages.

1 glass substrate 2 resin layer 3 metal layer 4 microstrip line 5 ground 6 coplanar waveguide line 7 ground

Claims (12)

a glass/resin laminate comprising a glass substrate and a resin layer in contact with at least one surface of the glass substrate;
and a metal layer in contact with the resin layer of the glass/resin laminate,
The surface of the glass substrate with which the resin layer abuts has an arithmetic mean roughness Ra of 1.0 μm or less,
The resin layer contains a tetrafluoroethylene-based polymer,
The glass substrate has a thickness of 50 to 5000 μm,
The resin layer has a thickness of 1 to 100 μm,
The metal layer has a thickness of 1 to 40 μm ,
The tetrafluoroethylene-based polymer has units based on tetrafluoroethylene and units based on at least one monomer selected from the group consisting of perfluoro(alkyl vinyl ether), hexafluoropropylene and fluoroalkylethylene,
The tetrafluoroethylene-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group,
A composite laminate , wherein the tetrafluoroethylene-based polymer is a melt-moldable polymer . 2. The glass/resin laminate according to claim 1, wherein the dielectric property L of the glass/resin laminate obtained by the following formula (1) and provided with resin layers in contact with both surfaces of the glass substrate is 0.001 to 0.020. Composite laminate.
Dielectric property L = (tan δ1 x t1 + 8 x tan δ2 x t21)/(t1 + 4 x t21)
formula (1)
(In the formula, tan δ1 is the dielectric loss tangent of the glass constituting the glass substrate at 28 GHz, t1 is the thickness [μm] of the glass substrate, tan δ2 is the dielectric loss tangent of the resin constituting the resin layer at 28 GHz, and t21 is the dielectric loss tangent of the glass substrate. It is the total thickness [μm] of each resin layer in contact with both surfaces) 2. The glass/resin laminate according to claim 1, wherein the dielectric property L of the glass/resin laminate provided with the resin layer in contact with one side of the glass substrate, which is obtained by the following formula (2), is 0.001 to 0.020. Composite laminate.
Dielectric property L=(tan δ1×t1+55×tan δ2×t22)/(t1+11×t22) Equation (2)
(In the formula, tan δ1 is the dielectric loss tangent of the glass constituting the glass substrate at 28 GHz, t1 is the thickness [μm] of the glass substrate, tan δ2 is the dielectric loss tangent of the resin constituting the resin layer at 28 GHz, and t22 is the dielectric loss tangent of the glass substrate. is the thickness [μm] of the resin layer in contact with one side) The composite laminate according to any one of claims 1 to 3, wherein the dielectric loss tangent of the glass constituting the glass substrate is 0.001 to 0.02 when measured at 28 GHz. The composite laminate according to any one of claims 1 to 4, wherein the glass substrate has a thickness of 200 to 600 µm, and the resin layer has a thickness of 20 to 80 µm. The composite laminate according to any one of claims 1 to 5, wherein the resin layer comprises an extruded film of a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer according to any one of claims 1 to 6, having a temperature range of 0.1 to 5.0 MPa at 260°C or lower and a melting point of higher than 260°C. A composite laminate as described. The composite laminate according to any one of claims 1 to 7 , wherein the metal layer has a maximum height roughness Rz of 7.0 µm or less on the side in contact with the resin layer. 9. The method according to any one of claims 1 to 8 , wherein the interface between the glass substrate and the resin layer has a peel strength of 5 N/cm or more, and the resin layer has a dielectric constant of 2.0 to 3.5. A composite laminate as described. The composite laminate according to any one of claims 1 to 9 , wherein said metal layer is patterned. The composite laminate according to claim 10 , which is an antenna. The composite laminate according to claim 10 , which is a semiconductor package substrate.

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