Patent Application
20250178027
The present disclosure relates to a film and a laminate.
In recent years, frequencies used in a communication equipment tend to be extremely high. In order to suppress transmission loss in a high frequency band, insulating materials used in a circuit board are required to have a lowered relative permittivity and a lowered dielectric loss tangent.
In the related art, polyimide is commonly used as the insulating material used in the circuit board, a liquid crystal polymer which has high heat resistance and low water absorption and is small in loss in the high frequency band has been attracted. In addition, in recent years, with the improvement of the performance of communication equipment, the size of blind vias and through-hole vias processed by multilayering or an UV laser has been reduced. Therefore, the layer for following and adhering to the circuit board is required to have excellent low dielectric characteristics and excellent UV laser workability.
As a film capacitor in the related art, for example, JP2020-178066A discloses a metalized film capacitor having a film for a dielectric with a surface energy of 15 to 24 mN/m and a metal thin film electrode on a surface of the film for a dielectric.
An object to be achieved by an embodiment of the present invention is to provide a film having excellent surface defect suppression properties in a low dielectric film.
Further, an object to be achieved by another embodiment of the present invention is to provide a laminate formed of the film.
The means for achieving the above-described objects include the following aspects.
<1> A film including: a layer A; and a layer B on at least one surface of the layer A, in which a dielectric loss tangent is 0.01 or less, and a surface free energy on a surface of the layer B on a side opposite to a layer A side is 30 mJ/m2 or less.
<2> A film including: a layer A; and a layer B on at least one surface of the layer A, in which a dielectric loss tangent is 0.01 or less, and an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B on a side opposite to a layer A side, is larger than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
<3> The film according to <1>, in which the surface free energy on the surface of the layer B on the side opposite to the layer A side is 15 mJ/m2 to 30 mJ/m2.
<4> The film according to any one of <1> to <3>, in which a ratio of an elastic modulus of the layer A at 160° C. to an elastic modulus of the layer B at 160° C. is 1.2 or more.
<5> The film according to any one of <1> to <4>, in which an elastic modulus of the layer B at 160° C. is 10 MPa or less.
<6> The film according to any one of <1> to <5>, in which a dielectric loss tangent of the layer B is 0.01 or less.
<7> The film according to any one of <1> to <6>, in which the layer B contains a liquid crystal polymer.
<8> The film according to any one of <1> to <7>, in which the layer B contains an aromatic polyester amide.
<9> The film according to any one of <1> to <8>, in which the layer B contains a thermoplastic resin having a constitutional unit having an aromatic hydrocarbon group.
<10> The film according to any one of <1> to <9>, in which a dielectric loss tangent of the layer A is 0.01 or less.
<11> The film according to any one of <1> to <10>, in which the layer A contains a liquid crystal polymer.
<12> The film according to any one of <1> to <11>, in which the layer A contains an aromatic polyester amide.
<13> A laminate including: the film according to any one of <1> to <12>; and a metal layer or a metal wire disposed on at least one surface of the film.
<14> A laminate including, in the following order: a layer A; a layer B; and a metal layer or a metal wire, in which a dielectric loss tangent is 0.01 or less, and a surface free energy on a surface of the layer B on a side opposite to a layer A side is 30 mJ/m2 or less.
<15> A laminate comprising, in the following order: a layer A; a layer B; and a metal layer or a metal wire, in which a dielectric loss tangent is 0.01 or less, and an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B on a side opposite to a layer A side, is larger than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
According to the embodiment of the present invention, it is possible to provide a film having excellent surface defect suppression properties in a low dielectric film.
Further, according to another aspect of the present invention, it is possible to provide a laminate formed of the film.
Hereinafter, the contents of the present disclosure will be described in detail. The description of configuration requirements below is made based on representative embodiments of the present disclosure in some cases, but the present disclosure is not limited to such embodiments.
Further, in the present specification, a numerical range shown using “to” indicates a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In a numerical range described in a stepwise manner in the present disclosure, an upper limit value or a lower limit value described in one numerical range may be replaced with an upper limit value or a lower limit value in another numerical range described in a stepwise manner. Further, in a numerical range described in the present disclosure, an upper limit value or a lower limit value described in the numerical range may be replaced with a value described in an example.
Further, in a case where substitution or unsubstitution is not noted in regard to the notation of a “group” (atomic group) in the present specification, the “group” includes not only a group that does not have a substituent but also a group having a substituent. For example, the concept of an “alkyl group” includes not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, the concept of “(meth)acryl” includes both acryl and methacryl, and the concept of “(meth)acryloyl” includes both acryloyl and methacryloyl.
Further, the term “step” in the present specification indicates not only an independent step but also a step which cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved. Further, in the present disclosure, “% by mass” has the same definition as that for “% by weight”, and “part by mass” has the same definition as that for “part by weight”.
Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) in the present disclosure are molecular weights converted using polystyrene as a standard substance by performing detection with a gel permeation chromatography (GPC) analysis apparatus using TSKgel SuperHM-H (trade name, manufactured by Tosoh Corporation) column, a solvent of pentafluorophenol (PFP) and chloroform at a mass ratio of 1:2, and a differential refractometer, unless otherwise specified.
Hereinafter, the present disclosure will be described in detail.
A first embodiment of the film according to the embodiment of the present disclosure includes a layer A, and a layer B on at least one surface of the layer A, in which a dielectric loss tangent is 0.01 or less, and a surface free energy on a surface of the layer B on a side opposite to a layer A side is 30 mJ/m2 or less.
A second embodiment of the film according to the embodiment of the present disclosure includes a layer A, and a layer B on at least one surface of the layer A, in which a dielectric loss tangent is 0.01 or less, and an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B on a side opposite to a layer A side, is larger than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
In the present specification, unless otherwise specified, the term “film according to the embodiment of the present disclosure” or “film” refers to both the first embodiment and the second embodiment, and the term “layer A” or the like refers to both the layer A and the like of the first embodiment and the second embodiment.
The present inventors have found that in a film having a plurality of layers in the related art, surface defects such as cissing and aggregation may occur during layer formation.
In the film according to the embodiment of the present disclosure, the dielectric loss tangent is 0.01 or less, the surface free energy on the surface of the layer B opposite to the layer A side is 30 mJ/m2 or less, or the ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on the surface of the layer B opposite to the layer A side is higher than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B, thereby appropriately adjusting the surface free energy on the surface of the layer B opposite to the layer A side, and the cissing on the surface during the layer formation and the aggregation of components in the layer are suppressed. As a result, it is possible to provide a film having excellent surface defect suppression properties in a low dielectric film having a dielectric loss tangent of 0.01 or less.
In the first embodiment of the film according to the embodiment of the present disclosure, the surface free energy of the surface of the above-described layer B on the side opposite to the above-described layer A side is 30 mJ/m2 or less, and from the viewpoint of image defect suppression property, void suppression property in wiring, and adhesiveness, the surface free energy is preferably 15 mJ/m2 to 30 mJ/m2 and more preferably 17 mJ/m2 to 26 mJ/m2.
In the second embodiment of the film according to the embodiment of the present disclosure, from the viewpoint of image defect suppression property, void suppression property in wiring, and adhesiveness, a surface free energy of the surface of the layer B on the side opposite to the layer A side is preferably 30 mJ/m2 or less, more preferably 15 mJ/m2 to 30 mJ/m2, still more preferably 18 mJ/m2 to 30 mJ/m2, and particularly preferably 25 mJ/m2 to 30 mJ/m2.
In the present disclosure, the surface free energy is calculated by the following method.
The contact angle of two types of samples is measured using a contact angle meter CA-A type (manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere of a room temperature of 23° C. and a relative humidity of 50% to 60%. Specifically, the contact angle of pure water with respect to the target surface and the contact angle of methylene iodide with respect to the target surface are measured. In the measurement of each contact angle, an average value of three measured values is defined as the contact angle. Using the contact angles of the two types of samples, the surface free energy γ (=γd+γp), which is the sum of the dispersive force γd and the polar force γp, is calculated by a geometric mean method based on Owens-Wendt. A specific calculation method and meanings of symbols are shown below.
In a case where γSL is a tension at an interface between the target surface and the liquid, the following Expression (1) is satisfied.
A state in which a liquid droplet is in contact with a smooth target surface at a contact angle (θ) is represented by the following expression (Young's equation).
In a case where Equation (1) and Equation (2) are combined, the following equation is obtained.
In practice, the contact angle (θ) of two types of samples of pure water and methylene iodide, the known surface free energy γL of the solution, and the respective components (γLd and γLp) are substituted into Expression (3), and the simultaneous equations are solved. As a result, the surface free energy (γS) of the target surface is calculated.
<Ion Intensity Derived from Fluorine Atom or Silicone Structure, Measured by Time-of-Flight Secondary Ion Mass Spectrometry>
In a second embodiment of the film according to the embodiment of the present disclosure, an ion intensity derived from a fluorine atom or a silicone structural element, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B opposite to the layer A side, is higher than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
In the first embodiment of the film according to the embodiment of the present disclosure, from the viewpoint of image defect suppression property, void suppression property in wiring, and adhesiveness, it is preferable that an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B opposite to the layer A side, is higher than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
In addition, from the viewpoint of image defect suppression property, void suppression property in the wiring line, and adhesiveness, a ratio (Iout/Iin) of an ion intensity Iout derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B of the film according to the embodiment of the present disclosure on a side opposite to the layer A side, to an ion intensity Iin derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B is preferably 1 or more, and more preferably 10 or more.
In the present disclosure, the ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, is a value calculated by the following method.
The measurement was carried out using time-of-flight secondary ion mass spectrometry (TOF-SIMS, TRIFT V nano TOF). Bi3+ (25 kV) was used as a primary ion source. The number of irradiated ions was set to 5×1010 ions/cm2 or less.
The detection of the fluorine atom and the silicone structure was carried out for F— and SiC3H9O−, respectively, and the detected value of the corresponding ion in a case where the detected total ion was standardized to 1 was defined as the ion intensity. The ion intensity Iin inside the layer B was measured by cutting the surface of the layer B on the side opposite to the above-described layer side by 0.5 μm and measuring the ion intensity of the exposed surface.
From the viewpoint of image defect suppression property, laser processing suitability and level difference followability, the elastic modulus of the layer A of the film according to the embodiment of the present disclosure at 160° C. is preferably 100 MPa to 2,500 MPa, more preferably 200 MPa to 2,000 MPa, still more preferably 300 MPa to 1,500 MPa, and particularly preferably 500 MPa to 1,000 MPa.
From the viewpoint of laser processing suitability and level difference followability, the elastic modulus of the layer B of the film according to the embodiment of the present disclosure at 160° C. is preferably 100 MPa or less, more preferably 10 MPa or less, still more preferably 0.001 MPa to 10 MPa, and particularly preferably 0.5 MPa to 5 MPa.
From the viewpoint of laser processing suitability and level difference followability, a ratio (MDA/MDB) of the elastic modulus MDA of the layer A at 160° C. to the elastic modulus MDB of the layer B at 160° C. in the film according to the embodiment of the present disclosure is preferably 1.2 or more, more preferably 5 to 1,000, still more preferably 10 to 800, and particularly preferably 100 to 600.
The elastic modulus in the present disclosure is measured by the following method.
First, the film or the laminate is cut in cross section with a microtome or the like, and the layer A or the layer B is specified from an image observed with an optical microscope. Next, the elastic modulus of the specified layer A or layer B was measured as an indentation elastic modulus using a nanoindentation method. The indentation elastic modulus is measured by using a microhardness tester (product name “DUH-W201”, manufactured by Shimadzu Corporation) to apply a load at a loading rate of 0.28 mN/sec with a Vickers indenter at 160° C., holding a maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/sec.
The measurement is also performed in the layers other than the layer A and the layer B. In addition, in a case where each layer is measured, an unnecessary layer may be scraped off with a razor or the like to produce an evaluation sample of only the target layer. In addition, in a case where it is difficult to take out the single film because the thickness of the layer is thin, a layer to be measured may be scraped off with a razor or the like, and the obtained powdery sample may be used.
The film according to the embodiment of the present disclosure has a layer A.
Further, examples of a method for detecting or determining the layer configuration, the thickness of each layer, and the like in the film include the following methods.
First, a cross-sectional sample of the film is cut out by a microtome, and a layer configuration and a thickness of each layer are determined with an optical microscope. In a case where the determination with an optical microscope is difficult, the determination may be obtained by performing morphological observation with a scanning electron microscope (SEM), or component analysis by a time-of-flight secondary ion mass spectrometry (TOF-SIMS) or the like.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, a dielectric loss tangent of the layer A is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.004 or less, and particularly preferably 0.003 or less. The lower limit value is not particularly set, and examples thereof include more than 0.
The dielectric loss tangent in the present disclosure is measured by the following method.
The dielectric loss tangent is measured by a resonance perturbation method at a frequency of 28 GHz. A 28 GHz cavity resonator (CP531 manufactured by KANTO Electronic Application and Development Inc.) is connected to a network analyzer (“E8363B” manufactured by Agilent Technology Co., Ltd.), a test piece is inserted into the cavity resonator, and the dielectric loss tangent of the film is measured from change in resonance frequency before and after insertion for 96 hours under an environment of a temperature of 25° C. and humidity of 60% RH.
In a case where each layer is measured, an unnecessary layer may be scraped off with a razor or the like to produce an evaluation sample of only the target layer. In addition, in a case where it is difficult to take out the single film because the thickness of the layer is thin, a layer to be measured may be scraped off with a razor or the like, and the obtained powdery sample may be used. In the present disclosure, the measurement of the dielectric loss tangent of the polymer is carried out according to the above-described measuring method of a dielectric loss tangent by identifying or isolating a chemical structure of the polymer constituting each layer and using a powdered sample of the polymer to be measured.
From the viewpoint of the dielectric loss tangent of the film and the laser processing suitability, the layer A preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
In addition, from the viewpoint of the dielectric loss tangent of the film and the laser processing suitability, the layer A preferably contains a polymer having an aromatic ring, and more preferably contains a polymer having an aromatic ring and having a dielectric loss tangent of 0.01 or less.
Further, from the viewpoint of the dielectric loss tangent of the film and the laser processing suitability, the layer A preferably contains a polymer and polymer particles, and more preferably contains a polymer having a dielectric loss tangent of 0.01 or less and particles of a polymer having a dielectric loss tangent of 0.01 or less.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the dielectric loss tangent of the polymer contained in the layer A of the film according to the embodiment of the present disclosure is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.004 or less, and particularly preferably 0.003 or less. The lower limit value is not particularly set, and examples thereof include more than 0.
From the viewpoints of the dielectric loss tangent of the film, the adhesiveness of the film to the metal (for example, the metal layer, the metal wire, or the like), and the heat resistance, the melting point Tm or the 5% mass-loss temperature Td of the polymer having a dielectric loss tangent of 0.01 or less is preferably 200° C. or higher, more preferably 250° C. or higher, still more preferably 280° C. or higher, and particularly preferably 300° C. or higher. The upper limit value thereof is not particularly limited, but is preferably 500° C. and more preferably 420° C.
The melting point Tm in the present disclosure is defined as a value measured by a differential scanning calorimetry (DSC) device. 5 mg of a sample is put into a measurement pan of the DSC, and a peak temperature of an endothermic peak which appears in a case where the sample is heated from 30° C. at 10° C./min in a nitrogen stream is defined as the Tm of the film.
In addition, the 5% mass-loss temperature Td in the present disclosure is measured with a thermogravimetric analysis (TGA) device. That is, a mass of the sample put into the measurement pan is defined as an initial value, and a temperature at which the mass is reduced by 5% by mass with respect to the initial value due to the heating is defined as the 5% mass-loss temperature Td.
From the viewpoints of the dielectric loss tangent of the film, the adhesiveness to the metal, and the heat resistance, the glass transition temperature Tg of the polymer having a dielectric loss tangent of 0.01 or less is preferably 150° C. or higher, and more preferably 200° C. or higher. The upper limit value thereof is not particularly limited, but is preferably 350° C. and more preferably 280° C.
The glass transition temperature Tg in the present disclosure is defined as a value measured by a differential scanning calorimetry (DSC) device.
A weight-average molecular weight Mw of the polymer having a dielectric loss tangent of 0.01 or less is preferably 1,000 or more, more preferably 2,000 or more, and particularly preferably 5,000 or more. In addition, the weight-average molecular weight Mw of the polymer having a dielectric loss tangent of 0.01 or less is preferably 50,000 or less, more preferably 20,000 or less, and particularly preferably less than 13,000.
In the present disclosure, the type of the polymer having a dielectric loss tangent of 0.01 or less is not particularly limited, and a known polymer can be used.
Examples of the polymer having a dielectric loss tangent of 0.01 or less include thermoplastic resins such as a liquid crystal polymer, a fluorine-based polymer, a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, aromatic polyether ketone, polycarbonate, polyethersulfone, polyphenylene ether and modified products thereof, and polyetherimide; elastomers such as a copolymer of glycidyl methacrylate and polyethylene; and thermosetting resins such as a phenol resin, an epoxy resin, a polyimide resin, and a cyanate resin.
Among these, from the viewpoint of dielectric loss tangent of the film, adhesiveness to the metal, and heat resistance, at least one polymer selected from the group consisting of a liquid crystal polymer, a fluorine-based polymer, a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyphenylene ether, and aromatic polyether ketone is preferable, and at least one polymer selected from the group consisting of a liquid crystal polymer and a fluorine-based polymer is more preferable.
From the viewpoint of adhesiveness and mechanical strength of the film, a liquid crystal polymer is preferable, and from the viewpoint of heat resistance and dielectric loss tangent, a fluorine-based polymer is preferable.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the layer A in the film according to the embodiment of the present disclosure preferably includes a liquid crystal polymer.
In the present disclosure, the type of the liquid crystal polymer is not particularly limited, and a known liquid crystal polymer can be used.
In addition, the liquid crystal polymer may be a thermotropic liquid crystal polymer which exhibits liquid crystallinity in a molten state, or may be a lyotropic liquid crystal polymer which exhibits liquid crystallinity in a solution state. Further, in a case where the liquid crystal polymer is a thermotropic liquid crystal polymer, the liquid crystal polymer is preferably a liquid crystal polymer which is molten at a temperature of 450° C. or lower.
Examples of the liquid crystal polymer include a liquid crystal polyester, a liquid crystal polyester amide in which an amide bond is introduced into the liquid crystal polyester, a liquid crystal polyester ether in which an ether bond is introduced into the liquid crystal polyester, and a liquid crystal polyester carbonate in which a carbonate bond is introduced into the liquid crystal polyester.
In addition, from the viewpoints of the dielectric loss tangent, the liquid crystallinity, and the thermal expansion coefficient of the film, the liquid crystal polymer is preferably a polymer having an aromatic ring, more preferably an aromatic polyester or an aromatic polyester amide, and particularly preferably an aromatic polyester amide.
Further, the liquid crystal polymer may be a polymer in which an imide bond, a carbodiimide bond, a bond derived from an isocyanate, such as an isocyanurate bond, or the like is further introduced into the aromatic polyester or the aromatic polyester amide.
Further, it is preferable that the liquid crystal polymer is a wholly aromatic liquid crystal polymer formed of only an aromatic compound as a raw material monomer.
Examples of the liquid crystal polymer include the following liquid crystal polymers.
Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine may be each independently replaced with a polycondensable derivative.
For example, the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid ester and aromatic dicarboxylic acid ester, by converting a carboxy group into an alkoxycarbonyl group or an aryloxycarbonyl group.
The aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid halide and aromatic dicarboxylic acid halide, by converting a carboxy group into a haloformyl group.
The aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid anhydride and aromatic dicarboxylic acid anhydride, by converting a carboxy group into an acyloxycarbonyl group.
Examples of a polymerizable derivative of a compound having a hydroxy group, such as an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic hydroxyamine, include a derivative (acylated product) obtained by acylating a hydroxy group and converting the acylated hydroxy group into an acyloxy group.
For example, the aromatic hydroxycarboxylic acid, the aromatic diol, and the aromatic hydroxyamine can be each replaced with an acylated product by acylating a hydroxy group and converting the acylated hydroxy group into an acyloxy group.
Examples of a polymerizable derivative of a compound having an amino group, such as an aromatic hydroxyamine or an aromatic diamine, include a derivative (acylated product) obtained by acylating an amino group and converting the acylated amino group to an acylamino group.
For example, the aromatic hydroxyamine and the aromatic diamine can be each replaced with an acylated product by acylating an amino group and converting the acylated amino group into an acylamino group.
From the viewpoint of liquid crystallinity, the dielectric loss tangent of the film, and adhesiveness to the metal, the liquid crystal polymer preferably has a constitutional unit represented by any of Formulae (1) to (3) (hereinafter, a constitutional unit represented by Formula (1) or the like may be referred to as a constitutional unit (1) or the like), more preferably has a constitutional unit represented by Formula (1), and particularly preferably has a constitutional unit represented by Formula (1), a constitutional unit represented by Formula (2), and a constitutional unit represented by Formula (3).
—O—Ar1—CO— Formula (1)
—CO—Ar2—CO— Formula (2)
—X—Ar3—Y— Formula (3)
In Formulae (1) to (3), Ar1 represents a phenylene group, a naphthylene group, or a biphenylylene group, Ar2 and Ar3 each independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by Formula (4), X and Y each independently represent an oxygen atom or an imino group, and hydrogen atoms in Ar1 to Ar3 may be each independently substituted with a halogen atom, an alkyl group, or an aryl group.
—Ar4—Z—Ar5— Formula (4)
In Formula (4), Ar4 and Ar5 each independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, and an n-decyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10.
Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. The number of carbon atoms in the aryl group is preferably 6 to 20.
In a case where the hydrogen atom is substituted with any of these groups, the number of each of substitutions in Ar1, Ar2, and Ar3 independently is preferably 2 or less and more preferably 1.
Examples of the alkylene group include a methylene group, a 1,1-ethanediyl group, a 1-methyl-1,1-ethanediyl group, a 1,1-butanediyl group, and a 2-ethyl-1,1-hexanediyl group. The number of carbon atoms in the alkylene group is preferably 1 to 10.
The constitutional unit (1) is a constitutional unit derived from an aromatic hydroxycarboxylic acid.
As the constitutional unit (1), an aspect in which Ar1 represents a p-phenylene group (constitutional unit derived from p-hydroxybenzoic acid), and an aspect in which Ar1 represents a 2,6-naphthylene group (constitutional unit derived from 6-hydroxy-2-naphthoic acid), or an aspect in which Ar1 represents a 4,4′-biphenylylene group (constitutional unit derived from 4′-hydroxy-4-biphenylcarboxylic acid) is preferable.
The constitutional unit (2) is a constitutional unit derived from an aromatic dicarboxylic acid.
As the constitutional unit (2), an aspect in which Ar2 represents a p-phenylene group (constitutional unit derived from terephthalic acid), an aspect in which Ar2 represents an m-phenylene group (constitutional unit derived from isophthalic acid), an aspect in which Ar2 represents a 2,6-naphthylene group (constitutional unit derived from 2,6-naphthalenedicarboxylic acid), or an aspect in which Ar2 represents a diphenylether-4,4′-diyl group (constitutional unit derived from diphenylether-4,4′-dicarboxylic acid) is preferable.
The constitutional unit (3) is a constitutional unit derived from an aromatic diol, an aromatic hydroxylamine, or an aromatic diamine.
As the constitutional unit (3), an aspect in which Ar3 represents a p-phenylene group (constitutional unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine), an aspect in which Ar3 represents an m-phenylene group (constitutional unit derived from isophthalic acid), or an aspect in which Ar3 represents a 4,4′-biphenylylene group (constitutional unit derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl, or 4,4′-diaminobiphenyl) is preferable.
A content of the constitutional unit (1) is preferably 30 mol % or more, more preferably 30 mol % to 80 mol %, still more preferably 30 mol % to 60 mol %, and particularly preferably 30 mol % to 40 mol % with respect to the total amount of all constitutional units (a value obtained by dividing the mass of each constitutional unit (also referred to as “monomer unit”) constituting the liquid crystal polymer by the formula weight of each constitutional unit to calculate an amount (mole) equivalent to the substance amount of each constitutional unit and adding up the amounts).
The content of the constitutional unit (2) is preferably 35 mol % or less, more preferably 10 mol % to 35 mol %, still more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol % with respect to the total amount of all constitutional units.
The content of the constitutional unit (3) is preferably 35 mol % or less, more preferably 10 mol % to 35 mol %, still more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol % with respect to the total amount of all constitutional units.
The heat resistance, the strength, and the rigidity are likely to be improved as the content of the constitutional unit (1) increases, but the solubility in a solvent is likely to be decreased in a case where the content thereof is extremely large.
A proportion of the content of the constitutional unit (2) to the content of the constitutional unit (3) is expressed as [content of constitutional unit (2)]/[content of constitutional unit (3)] (mol/mol), and is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and still more preferably 0.98/1 to 1/0.98.
The liquid crystal polymer may have two or more kinds of each of the constitutional units (1) to (3) independently. In addition, the liquid crystal polymer may have a constitutional unit other than the constitutional units (1) to (3), but the content thereof is preferably 10 mol % or less and more preferably 5 mol % or less with respect to the total amount of all the constitutional units.
From the viewpoint of solubility in a solvent, the liquid crystal polymer preferably has, as the constitutional unit (3), a constitutional unit (3) in which at least one of X or Y is an imino group, that is, preferably has as the constitutional unit (3), at least one of a constitutional unit derived from an aromatic hydroxylamine or a constitutional unit derived from an aromatic diamine, and it is more preferable to have only a constitutional unit (3) in which at least one of X or Y is an imino group.
It is preferable that the liquid crystal polymer is produced by melt-polymerizing raw material monomers corresponding to the constitutional units constituting the liquid crystal polymer. The melt polymerization may be carried out in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole; and preferred examples thereof include nitrogen-containing heterocyclic compounds. The melt polymerization may be further carried out by solid-state polymerization as necessary.
The lower limit value of a flow start temperature of the liquid crystal polymer is preferably 180° C. or higher, more preferably 200° C. or higher, and still more preferably 250° C. or higher, and the upper limit value of the flow start temperature thereof is preferably 350° C., more preferably 330° C., and still more preferably 310° C. In a case where the flow start temperature of the liquid crystal polymer is within the above-described range, the solubility, the heat resistance, the strength, and the rigidity are excellent, and the viscosity of the solution is appropriate.
The flow start temperature, also referred to as a flow temperature, is a temperature at which a viscosity of 4,800 Pa·s (48,000 poises) is exhibited in a case where the liquid crystal polymer is melted and extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm while the temperature is raised at a rate of 4° C./min under a load of 9.8 MPa (100 kg/cm2) using a capillary rheometer and is a guideline for the molecular weight of the liquid crystal polymer (see p. 95 of “Liquid Crystal Polymers-Synthesis/Molding/Applications-”, written by Naoyuki Koide, CMC Corporation, Jun. 5, 1987).
In addition, a weight-average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, still more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000. In a case where the weight-average molecular weight of the liquid crystal polymer is within the above-described range, a film after heat treatment is excellent in thermal conductivity, heat resistance, strength, and rigidity in the thickness direction.
From the viewpoint of heat resistance and mechanical strength, the polymer having a dielectric loss tangent of 0.01 or less is preferably a fluorine-based polymer.
In the present disclosure, the type of the fluorine-based polymer used as the polymer having a dielectric loss tangent of 0.01 or less is not particularly limited as long as the dielectric loss tangent thereof is 0.01 or less, and a known fluorine-based polymer can be used.
Examples of the fluorine-based polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, a perfluoroalkoxy fluororesin, a tetrafluoroethylene/hexafluoropropylene copolymer, an ethylene/tetrafluoroethylene copolymer, and an ethylene/chlorotrifluoroethylene copolymer.
Among these, polytetrafluoroethylene is preferable.
In addition, examples of the fluorine-based polymer include a fluorinated α-olefin monomer, that is, an α-olefin monomer containing at least one fluorine atom; and a homopolymer and a copolymer containing a constitutional unit derived from a non-fluorinated ethylenically unsaturated monomer reactive to the fluorinated α-olefin monomer, as necessary.
Examples of the fluorinated α-olefin monomer include CF2—CF2, CHF—CF2, CH2—CF2, CHCI═CHF, CCIF═CF2, CCl2═CF2, CCIF═CCIF, CHF═CC12, CH2═CCIF, CCl2═CCIF, CF3CF═CF2, CF3CF═CHF, CF3CH═CF2, CF3CH═CH2, CHF2CH═CHF, CF3CF═CF2, and perfluoro (alkyl having 2 to 8 carbon atoms) vinyl ether (for example, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether). Among these, at least one monomer selected from the group consisting of tetrafluoroethylene (CF2═CF2), chlorotrifluoroethylene (CCIF═CF2), (perfluorobutyl)ethylene, vinylidene fluoride (CH2═CF2), and hexafluoropropylene (CF2═CFCF3) is preferable.
Examples of the non-fluorinated monoethylenically unsaturated monomer include ethylene, propylene, butene, and an ethylenically unsaturated aromatic monomer (for example, styrene and α-methylstyrene).
The fluorinated α-olefin monomer may be used alone or in combination of two or more thereof.
In addition, the non-fluorinated ethylenically unsaturated monomer may be used alone or in combination of two or more thereof.
Examples of the fluorine-based polymer include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE), poly(hexafluoropropylene), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-ethylene-propylene), poly(tetrafluoroethylene-hexafluoropropylene) (FEP), poly(tetrafluoroethylene-propylene) (FEPM), poly(tetrafluoroethylene-perfluoropropylene vinyl ether), poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA) (for example, poly(tetrafluorocthylene-perfluoropropyl vinyl ether)), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-chlorotrifluoroethylene), perfluoropolyether, perfluorosulfonic acid, and perfluoropolyoxetane.
The fluorine-based polymer may be used alone or in combination of two or more thereof.
The fluorine-based polymer is preferably at least one of FEP, PFA, ETFE, or PTFE. The FEP is available from Du Pont as the trade name of TEFLON (registered trademark) FEP or from DAIKIN INDUSTRIES, LTD. as the trade name of NEOFLON FEP; and the PFA is available from DAIKIN INDUSTRIES, LTD. as the trade name of NEOFLON PFA, from Du Pont as the trade name of TEFLON (registered trademark) PFA, or from Solvay Solexis as the trade name of HYFLON PFA.
The fluorine-based polymer preferably includes PTFE. The PTFE can be included as a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination including one or both of these. The partially modified PTFE homopolymer preferably contains a constitutional unit derived from a comonomer other than tetrafluoroethylene in an amount of less than 1% by mass based on the total mass of the polymer.
The fluorine-based polymer may be a crosslinkable fluoropolymer having a crosslinkable group. The crosslinkable fluoropolymer can be crosslinked by a known crosslinking method in the related art. One of the representative crosslinkable fluoropolymers is a fluoropolymer having a (meth)acryloxy group. For example, the crosslinkable fluoropolymer can be represented by Formula:
H2C—CR′COO—(CH2)n—R—(CH2)n—OOCR′═CH2
In the formula, R is a fluorine-based oligomer chain having two or more constitutional units derived from the fluorinated α-olefin monomer or the non-fluorinated monoethylenically unsaturated monomer, R′ is H or —CH3, and n is 1 to 4. R may be a fluorine-based oligomer chain having a constitutional unit derived from tetrafluoroethylene.
In order to initiate a radical crosslinking reaction through the (meth)acryloxy group in the fluorine-based polymer, by exposing the fluoropolymer having a (meth)acryloxy group to a free radical source, a crosslinked fluoropolymer network can be formed. The free radical source is not particularly limited, and suitable examples thereof include a photoradical polymerization initiator and an organic peroxide. Appropriate photoradical polymerization initiators and organic peroxides are well known in the art. The crosslinkable fluoropolymer is commercially available, and examples thereof include Viton B manufactured by Du Pont.
—Polymerized Substance of Compound which has Cyclic Aliphatic Hydrocarbon Group and Group Having Ethylenically Unsaturated Bond—
The polymer having a dielectric loss tangent of 0.01 or less may be a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
Examples of the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include thermoplastic resins having a constitutional unit formed from a monomer having a cyclic olefin such as norbornene and a polycyclic norbornene-based monomer, which is also referred to as a thermoplastic cyclic olefin-based resin.
The polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a ring-opened polymer of the above-described cyclic olefin, a hydrogenated product of a ring-opened copolymer using two or more cyclic olefins, or an addition polymer of a cyclic olefin and a linear olefin or aromatic compound having an ethylenically unsaturated bond such as a vinyl group. In addition, a polar group may be introduced into the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
The polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more thereof.
A ring structure of the cyclic aliphatic hydrocarbon group may be a single ring, a fused ring in which two or more rings are fused, or a crosslinked ring.
Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isophorone ring, a norbornane ring, and a dicyclopentane ring.
The compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
The number of cyclic aliphatic hydrocarbon groups in the compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be 1 or more, and may be 2 or more.
The polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a polymer obtained by polymerizing at least one compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, may be a polymerized substance of two or more kinds of the compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, or may be a copolymer with other ethylenically unsaturated compounds having no cyclic aliphatic hydrocarbon group.
In addition, the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
The layer A preferably contains a polyphenylene ether.
In a case where heat curing is performed after film formation, from the viewpoint of heat resistance and film-forming property, a weight-average molecular weight (Mw) of the polyphenylene ether is preferably 500 to 5,000 and more preferably 500 to 3,000. In addition, in a case where the heat curing is not performed, the weight-average molecular weight (Mw) of the polyphenylene ether is not particularly limited, but is preferably 3,000 to 100,000 and more preferably 5,000 to 50,000.
In the polyphenylene ether, from the viewpoint of dielectric loss tangent and heat resistance, the average number of molecular terminal phenolic hydroxyl groups per molecule (the number of terminal hydroxyl groups) is preferably 1 to 5 and more preferably 1.5 to 3.
The number of hydroxyl groups or the number of the phenolic hydroxyl groups in the polyphenylene ether can be found, for example, from a standard value of a product of the polyphenylene ether. In addition, examples of the number of terminal hydroxyl groups or the number of terminal phenolic hydroxyl groups include a numerical value representing an average value of hydroxyl groups or phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mol of the polyphenylene ether.
The polyphenylene ether may be used alone or in combination of two or more thereof.
Examples of the polyphenylene ether include a polyphenylene ether including 2,6-dimethylphenol and at least one of bifunctional phenol or trifunctional phenol, and a compound mainly including the polyphenylene ether, such as poly(2,6-dimethyl-1,4-phenylene oxide). More specifically, for example, a compound having a structure represented by Formula (PPE) is preferable.
In Formula (PPE), X represents an alkylene group having 1 to 3 carbon atoms or a single bond, m represents an integer of 0 to 20, n represents an integer of 0 to 20, and the sum of m and n represents an integer of 1 to 30.
Examples of the alkylene group in X described above include a dimethylmethylene group.
The polymer having a dielectric loss tangent of 0.01 or less may be an aromatic polyether ketone.
The aromatic polyether ketone is not particularly limited, and a known aromatic polyether ketone can be used.
The aromatic polyether ketone is preferably a polyether ether ketone.
The polyether ether ketone is one type of the aromatic polyether ketone, and is a polymer in which bonds are arranged in the order of an ether bond, an ether bond, and a carbonyl bond (ketone). It is preferable that the bonds are linked to each other by a divalent aromatic group.
The aromatic polyether ketone may be used alone or in combination of two or more thereof.
Examples of the aromatic polyether ketone include polyether ether ketone (PEEK) having a chemical structure represented by Formula (P1), polyether ketone (PEK) having a chemical structure represented by Formula (P2), polyether ketone ketone (PEKK) having a chemical structure represented by Formula (P3), polyether ether ketone ketone (PEEKK) having a chemical structure represented by Formula (P4), and polyether ketone ether ketone ketone (PEKEKK) having a chemical structure represented by Formula (P5).
From the viewpoint of mechanical properties, each n of Formulae (P1) to (P5) is preferably 10 or more and more preferably 20 or more. On the other hand, from the viewpoint that the aromatic polyether ketone can be easily produced, n is preferably 5,000 or less and more preferably 1,000 or less. That is, n is preferably 10 to 5,000 and more preferably 20 to 1,000.
The polymer having a dielectric loss tangent of 0.01 or less is preferably a polymer soluble in a specific organic solvent (hereinafter, also referred to as “soluble polymer”).
Specifically, the soluble polymer according to the embodiment of the present disclosure is a liquid crystal polymer in which 0.1 g or more thereof is dissolved at 25° C. in 100 g of at least one solvent selected from the group consisting of N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, dichloroethane, chloroform, N,N-dimethylacetamide, γ-butyrolactone, dimethylformamide, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether.
The layer A may contain only one kind of polymer having a dielectric loss tangent of 0.01 or less, or may contain two or more kinds thereof.
From the viewpoint of the dielectric loss tangent of the film and the adhesiveness to the metal, the content of the polymer having a dielectric loss tangent of 0.01 or less, which is preferably a liquid crystal polymer, in the layer A is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, still more preferably 30% by mass to 100% by mass, and particularly preferably 40% by mass to 100% by mass with respect to the total mass of the layer A.
From the viewpoint of dielectric loss tangent of the film and adhesiveness to the metal, the content of the polymer having a dielectric loss tangent of 0.01 or less, which is preferably a liquid crystal polymer, in the film is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, still more preferably 40% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass with respect to the total mass of the film.
The content of the polymer having a dielectric loss tangent of 0.01 or less also includes the content of the polymer having a particulate dielectric loss tangent of 0.01 or less, which will be described later, is.
The layer A may contain a filler from the viewpoint of a thermal expansion coefficient and adhesiveness to the metal.
The filler may be particulate or fibrous, and may be an inorganic filler or an organic filler. However, from the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, an organic filler is preferable.
In the film according to the embodiment of the present disclosure, from the viewpoint of the thermal expansion coefficient and the adhesiveness to the metal, the number density of the filler is preferably larger inside the film than the surface of the film.
Here, the surface of the film refers to a surface (surface in contact with air or substrate) of the film outside, and a smaller one of a range of 3 μm in a depth direction from the most surface or a range of 10% or less of the thickness of the entire film from the most surface is defined as the “surface”. The inside of the film refers to a portion other than the surface of the film, that is, a surface (a surface not in contact with air or a substrate) inside the film, and is not limited, but in a range of ±1.5 μm from the center in a thickness direction of the film or in a range of ±5% of the total thickness from the center in the thickness direction of the film, one having a smaller numerical value is defined as “inside”.
As the organic filler, a known organic filler can be used.
Examples of a material of the organic filler include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, cured epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, a liquid crystal polymer, and a material containing two or more kinds of these.
In addition, the organic filler may be fibrous, such as nanofibers, or may be hollow resin particles.
Among these, as the organic filler, from the viewpoint of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, fluororesin particles, polyester-based resin particles, polyethylene particles, liquid crystal polymer particles, or cellulose-based resin nanofibers are preferable; polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles are more preferable; and liquid crystal polymer particles are particularly preferable. Here, the liquid crystal polymer particles are not limited, but refer to particles obtained by polymerizing a liquid crystal polymer and crushing the liquid crystal polymer with a crusher or the like to obtain powdery liquid crystal. The liquid crystal polymer particles are preferably smaller than the thickness of each layer.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the average particle diameter of the organic filler is preferably 5 nm to 20 μm and more preferably 100 nm to 10 μm.
As the inorganic filler, a known inorganic filler can be used.
Examples of a material of the inorganic filler include BN, Al2O3, AlN, TiO2, SiO2, barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and a material containing two or more of these.
Among these, as the inorganic filler, from the viewpoint of thermal expansion coefficient and adhesiveness to the metal, metal oxide particles or fibers are preferable, silica particles, titania particles, or glass fibers are more preferable, and silica particles or glass fibers are particularly preferable.
An average particle diameter of the inorganic filler is preferably approximately 20% to approximately 40% of the thickness of a layer A, and for example, the average particle diameter may be selected from 25%, 30%, or 35% of the thickness of the layer A. In a case where the particles or fibers are flat, the average particle diameter indicates a length in a short side direction.
In addition, from the viewpoint of thermal expansion coefficient and adhesiveness to the metal, the average particle diameter of the inorganic filler is preferably 5 nm to 20 μm, more preferably 10 nm to 10 μm, still more preferably 20 nm to 1 μm, and particularly preferably 25 nm to 500 nm.
The layer A may contain only one or two or more kinds of the fillers.
From the viewpoint of adhesiveness to the metal, it is preferable that a content of the filler in the layer A is smaller than a content of the filler in the layer B.
In addition, from the viewpoint of laser processing suitability and adhesiveness to the metal, the content of the filler in the layer A is preferably 10% by mass to 90% by mass and more preferably 30% by mass to 80% by mass with respect to the total mass of the layer A.
A content of a filler such as polyethylene and an olefin-based elastomer is, for example, preferably 50% by volume to 90% by volume, and more preferably 75% by volume to 85% by volume. In this case, the content of the filler in the layer A is preferably 55% by mass to 90% by mass, and more preferably 80% by mass to 85% by mass with respect to the total mass of the layer A.
The layer A may contain an additive other than the above-described components.
Known additives can be used as other additives. Specific examples of the other additives include a curing agent, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorbing agent, a flame retardant, and a colorant.
In addition, the layer A may contain other resins other than the above-described polymer and polymer particles as other additives.
Examples of other resins include thermoplastic resins such as polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyethersulfone, polyphenylene ether and a modified product thereof, and polyetherimide; elastomers such as a copolymer of glycidyl methacrylate and polyethylene; and thermosetting resins such as a phenol resin, an epoxy resin, a polyimide resin, and a cyanate resin.
The total content of the other additives in the layer A is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the content of the polymer having a dielectric loss tangent of 0.01 or less.
From the viewpoints of the dielectric loss tangent of the film and the adhesiveness to the metal, the average thickness of the layer A is preferably thicker than the average thickness of the layer B.
From the viewpoint of dielectric loss tangent of the film and adhesiveness to the metal, a value of TA/TB, which is a ratio of the average thickness TA of the layer A to the average thickness TB of the layer B, is preferably 0.8 to 10, more preferably 1 to 5, still more preferably more than 1 and 3 or less, and particularly preferably more than 1 and 2 or less.
In addition, the average thickness of the layer A is not particularly limited, but from the viewpoint of dielectric loss tangent of the film and adhesiveness to the metal, the average thickness thereof is preferably 5 μm to 90 μm, more preferably 10 μm to 70 μm, and particularly preferably 15 μm to 60 μm.
A measuring method of the average thickness of each layer in the film according to the embodiment of the present disclosure is as follows.
The thickness of each layer is evaluated by cutting the film with a microtome and observing the cross section with an optical microscope. Three or more sites of the cross-sectional sample are cut out, the thickness is measured at three or more points in each cross section, and the average value thereof is defined as the average thickness.
The film according to the embodiment of the present disclosure includes a layer B on at least one surface of the layer A.
From the viewpoint of the dielectric loss tangent of the film and the adhesiveness to the metal, the layer B preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the dielectric loss tangent of the layer B is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.004 or less, and particularly preferably 0.003 or less. The lower limit values of both cases are not particularly set, and examples thereof include a value of more than 0.
From the viewpoint of image defect suppression properties, void suppression properties of wiring lines, and adhesiveness, the layer B preferably contains a fluorine-based surfactant or a silicone-based surfactant.
The fluorine-based surfactant is not particularly limited provided that it is a surfactant having a fluorine-containing group as a hydrophobic group, and examples thereof include perfluorooctane sulfonic acid and perfluorocarboxylic acid.
Specific examples of the fluorine-based surfactant include MEGAFACE series manufactured by DIC Corporation, such as MEGAFACE F-444, SURFLON series manufactured by AGC SEIMI CHEMICAL Co., Ltd., such as SURFLON S-221, and FTERGENT series manufactured by NEOS COMPANY LIMITED, such as FTERGENT 100.
Further, the surfactant may be a polymer, and examples thereof include an acrylic polymer containing, as an essential component, a monomer containing a fluorinated alkyl group, and a siloxane-based polymer in which a chain skeleton consists of a Si—O bond.
Examples of the silicone-based surfactant include a linear polymer consisting of a siloxane bond and a modified siloxane polymer with an organic group introduced in the side chain or the terminal.
Specific examples of the silicone-based surfactant include DOWSIL (product name) 8032 ADDITIVE, TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DCIIPA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (all manufactured by Toray Dow Corning Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.); and BYK300, BYK307, BYK323, BYK330 (all manufactured by BYK Additives & Instruments).
The layer B may contain only one kind of fluorine-based surfactant, or may contain two or more kinds thereof.
The layer B may contain only one kind of silicone-based surfactant, or may contain two or more kinds thereof.
In addition, from the viewpoint of image defect suppression property, void suppression property of the wiring, and adhesiveness, the total content of the fluorine-based surfactant and the silicone-based surfactant in the layer B is preferably 0.001% by mass to 10% by mass, and more preferably 0.002% by mass to 2% by mass with respect to the total mass of the layer B. The content of the fluorine-based surfactant and the silicone-based surfactant in the layer B is particularly preferably 0.005% by mass to 0.5% by mass.
The preferred aspect of the polymer having a dielectric loss tangent of 0.01 or less, which is used for the layer B, is the same as the preferred aspect of the polymer having a dielectric loss tangent of 0.01 or less, which is used for the layer A, except as described later.
The polymer having a dielectric loss tangent of 0.01 or less, which is contained in the layer B, may be the same as or different from the polymer having a dielectric loss tangent of 0.01 or less, which is contained in the layer A, but from the viewpoint of the adhesiveness between the layer A and the layer B and the laser processing suitability, the layer B preferably contains the same polymer as the polymer having a dielectric loss tangent of 0.01 or less, which is contained in the layer A.
The layer B may contain only one kind of polymer having a dielectric loss tangent of 0.01 or less, or may contain two or more kinds thereof.
A content proportion of the polymer having a dielectric loss tangent of 0.01 or less in the layer B is preferably equal to or larger than a content proportion of the polymer having a dielectric loss tangent of 0.01 or less in the layer A.
From the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the adhesiveness to the metal, the content of the polymer having a dielectric loss tangent of 0.01 or less in the layer B is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, and particularly preferably 40% by mass to 100% by mass with respect to the total mass of the layer B.
In addition, the layer B may contain a polymer other than the polymer having a dielectric loss tangent of 0.01 or less as a binder polymer.
From the viewpoints of the dielectric loss tangent, the laser processing suitability, and the level difference followability of the film, preferred examples of the other polymer include a thermoplastic resin including a thermoplastic elastomer. The elastomer refers to a polymer compound exhibiting elastic deformation. That is, the elastomer corresponds to a polymer compound having a property of being deformed according to an external force in a case where the external force is applied and of being recovered to an original shape in a short time in a case where the external force is removed.
Examples of the thermoplastic resin include a polyurethane resin, a polyester resin, a (meth)acrylic resin, a polystyrene resin, a fluororesin, a polyimide resin, a fluorinated polyimide resin, a polyamide resin, a polyamideimide resin, a polyether imide resin, a cellulose acylate resin, a polyether ether ketone resin, a polycarbonate resin, a polyolefin resin (for example, a polyethylene resin, a polypropylene resin, a resin consisting of a cyclic olefin copolymer, and an alicyclic polyolefin resin), a polyarylate resin, a polyether sulfone resin, a polysulfone resin, a fluorene ring-modified polycarbonate resin, an alicyclic ring-modified polycarbonate resin, and a fluorene ring-modified polyester resin.
The thermoplastic elastomer is not particularly limited, and examples thereof include an elastomer having a constitutional repeating unit derived from styrene (polystyrene-based elastomer), a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacryl-based elastomer, a silicone-based elastomer, and a polyimide-based elastomer. The thermoplastic elastomer may be a hydride.
Examples the polystyrene-based elastomer include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), a polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymer (SEPS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer (SEEPS), and hydrides thereof.
Among these, from the viewpoint of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the layer B preferably contains, as other polymers, a thermoplastic resin having an aromatic hydrocarbon group-containing constitutional unit, more preferably contains a polystyrene-based elastomer, and particularly preferably contains a hydrogenated styrene-ethylene-butylene-styrene block copolymer.
In addition, as the other polymer, a hydrogenated polystyrene-based elastomer is preferable from the viewpoints of the dielectric loss tangent, the laser processing suitability, and the level difference followability of the film.
The content of the other polymer other than the polymer having a dielectric loss tangent of 0.01 or less is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film, the laser processing suitability, and the adhesiveness to the metal, the content is preferably 10% by mass to 100% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 10% by mass to 60% by mass with respect to the total mass of the layer B.
From the viewpoints of the dielectric loss tangent of the film, laser processing suitability, adhesiveness to a metal, and level difference followability, it is more preferable that the layer B includes a filler.
Preferred aspects of the filler which is used in the layer B are the same as the preferred aspects of the filler which is used in the layer A, except as described below.
In addition, as the filler used in the layer B, the particles of the above-described thermoplastic resin are also preferably mentioned.
Further, from the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, at least one of the binder polymer or the filler contained in the layer B is preferably a polymer having a dielectric loss tangent of 0.01 or less, and more preferably a liquid crystal polymer.
In addition, from the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the layer B preferably contains crosslinked resin particles as the filler.
The crosslinked resin in the crosslinked resin particles is not particularly limited, and a known crosslinked resin can be used. For example, the crosslinked resin may be a crosslinked resin obtained by using a crosslinking agent during polymerization or a crosslinked resin obtained by reacting a crosslinking agent with a resin.
Among these, as the crosslinked resin particles, from the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the thermoplastic elastomer particles are preferable, polystyrene-based elastomer particles are more preferable, and hydrogenated polystyrene-based elastomer is particularly preferable.
The layer B may contain only one or two or more kinds of the fillers.
In addition, from the viewpoint of laser processing suitability and adhesiveness to the metal, the content of the filler in the layer B is preferably 10% by mass to 90% by mass and more preferably 20% by mass to 80% by mass with respect to the total mass of the layer B. The layer B may contain an additive other than those described above.
Preferred aspects of other additives which are used in the layer B are the same as the preferred aspects of other additives which are used in the layer A, except as described below.
In addition, an average thickness of the layer B is not particularly limited, but from the viewpoints of the dielectric loss tangent of the film, the laser processing suitability, and the level difference followability, the average thickness is preferably 1 μm to 90 μm, more preferably 5 μm to 60 μm, and particularly preferably 10 μm to 40 μm.
The film according to the embodiment of the present disclosure includes the layer B, and thus, a film having excellent adhesiveness to the metal can be obtained. For example, in a case where the layer A has a filler, it is presumed that, by including the layer B and the layer A brittle due to the addition of the filler, the surface of the film is improved, and effects such as improvement in adhesiveness are obtained.
In addition, the layer B is preferably a surface layer (outermost layer). For example, in a case where the film is used as a laminate (laminated plate with a metal layer) having a layer configuration of metal layer/layer A/layer B, another metal layer or laminated plate with a metal layer may be further disposed on the layer B side. In this case, interface destruction between the layer B and another metal layer in the laminate is suppressed, and the adhesiveness to the metal is improved.
In addition, it is preferable that the polymer contained in the layer B contains a polymer having a higher breaking strength (toughness) that the polymer contained in the layer A.
The breaking strength is measured by the following method.
A sample including the polymer to be measured is produced, and using a universal tensile tester “STM T50BP” manufactured by Toyo Baldwin Co., Ltd., a stress against elongation is measured at a tensile rate of 10%/min in an atmosphere of 25° C. and 60% RH to obtain the breaking strength.
From the viewpoint of strength and electrical characteristics (characteristic impedance) in a case of being laminated with the metal layer, an average thickness of the film according to the embodiment of the present disclosure is preferably 6 μm to 200 μm, more preferably 12 μm to 100 μm, and particularly preferably 20 μm to 80 μm.
The average thickness of the film is measured at optional five sites using an adhesive film thickness meter, for example, an electronic micrometer (product name, “KG3001A”, manufactured by Anritsu Corporation), and the average value of the measured values is defined as the average thickness of the film.
From the viewpoint of dielectric constant, the dielectric loss tangent of the film according to the embodiment of the present disclosure is preferably 0.008 or less, more preferably 0.005 or less, still more preferably 0.004 or less, and particularly preferably more than 0 and 0.003 or less.
A manufacturing method of the film according to the embodiment of the present disclosure is not particularly limited, and a known method can be referred to.
Suitable examples of the manufacturing method of the film according to the embodiment of the present disclosure include a co-casting method, a multilayer coating method, and a co-extrusion method. Among these, the co-casting method is particularly preferable for formation of a relatively thin film, and the co-extrusion method is particularly preferable for formation of a thick film.
In a case where the film is manufactured by the co-casting method or the multilayer coating method, it is preferable that the co-casting method or the multilayer coating method is performed by using a composition for forming the layer A, a composition for forming the layer B, or the like obtained by dissolving or dispersing components of each layer, such as the polymer having a dielectric loss tangent of 0.01 or less or the liquid crystal polymer, and the compound having a functional group, in a solvent.
Examples of the solvent include halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone and cyclohexanone; esters such as ethyl acetate and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoramide and tri-n-butyl phosphate. Among these, two or more kinds thereof may be used in combination.
The solvent preferably contains an aprotic compound (particularly, an aprotic compound having no halogen atom) for low corrosiveness and easiness to handle. A proportion of the aprotic compound to the whole solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. In addition, from the viewpoint of easily dissolving the liquid crystal polymer, as the above-described aprotic compound, it is preferable to contain an amide such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, and N-methylpyrrolidone, or an ester such as γ-butyrolactone; and it is more preferable to contain N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.
In addition, as the solvent, it is preferable to contain a compound having a dipole moment of 3 to 5, because the above-described polymer such as the liquid crystal polymer can be easily dissolved. A proportion of the compound having a dipole moment of 3 to 5 to the whole solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
It is preferable to use the compound having a dipole moment of 3 to 5 as the above-described aprotic compound.
In addition, as the solvent, it is preferable to contain a compound having a boiling point of 220° C. or lower at 1 atm, because the solvent is easily removed. A proportion of the compound having a boiling point of 220° C. or lower at 1 atm to the whole solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
It is preferable to use the compound having a boiling point of 220° C. or lower at 1 atm as the above-described aprotic compound.
In addition, in a case where the film according to the embodiment of the present disclosure is manufactured by the above-described manufacturing method such as the co-casting method, the multilayer coating method, and the co-extrusion method, the film may have a support. In addition, in a case where the metal layer (metal foil) or the like used in the laminate described later is used as the support, the support may be used as it is without being peeled off.
Examples of the support include a metal drum, a metal band, a glass plate, a resin film, and a metal foil. Among these, a metal drum, a metal band, or a resin film is preferable.
Examples of the resin film include a polyimide (PI) film, and examples of commercially available products thereof include U-PILEX S and U-PILEX R (manufactured by UBE Corporation), KAPTON (manufactured by Du Pont-Toray Co., Ltd.), and IF30, IF70, and LV300 (manufactured by SKC Kolon PI, Inc.).
In addition, the support may have a surface treatment layer formed on the surface so that the support can be easily peeled off. Hard chrome plating, a fluororesin, or the like can be used as the surface treatment layer.
An average thickness of the support is not particularly limited, but is preferably 25 μm or more and 75 μm or less and more preferably 50 μm or more and 75 μm or less.
In addition, a method for removing at least a part of the solvent from a cast or applied film-like composition (a casting film or a coating film) is not particularly limited, and a known drying method can be used.
In the film according to the embodiment of the present disclosure, stretching can be combined as appropriate from the viewpoint of controlling molecular alignment and adjusting linear expansion coefficient and mechanical properties. The stretching method is not particularly limited, and a known method can be referred to, and the stretching method may be carried out in a solvent-containing state or in a dry film state. The stretching in the solvent-containing state may be carried out by gripping and stretching the film, or may be carried out by utilizing self-contraction due to drying without stretching. The stretching is particularly effective for the purpose of improving the breaking elongation and the breaking strength, in a case where brittleness of the film is reduced by addition of an inorganic filler or the like.
In addition, the manufacturing method of the film according to the embodiment of the present disclosure may include a step of polymerizing the film by light or heat, as necessary.
A light irradiation means and a heat application means are not particularly limited, and a known light irradiation means such as a metal halide lamp and a known heat application unit such as a heater can be used.
Light irradiation conditions and heat application conditions are not particularly limited, and the polymerization can be carried out at a desired temperature and time and in a known atmosphere.
The manufacturing method of the film according to the embodiment of the present disclosure preferably includes a step of subjecting the film to a heat treatment (annealing).
Specifically, from the viewpoint of dielectric loss tangent and peel strength, the heat treatment temperature in the above-described step of heat-treating is preferably 260° C. to 370° C., more preferably 280° C. to 360° C., and still more preferably 300° C. to 350° C. The heat treatment time is preferably 15 minutes to 10 hours and more preferably 30 minutes to 5 hours.
In addition, the manufacturing method of the film according to the embodiment of the present disclosure may include other known steps as necessary.
The film according to the embodiment of the present disclosure can be used for various applications. Among the various applications, the film can be used suitably as a film for an electronic component such as a printed wiring board and more suitably for a flexible printed circuit board.
In addition, the film according to the embodiment of the present disclosure can be suitably used as a metal adhesive film.
The laminate according to the embodiment of the present disclosure may be a laminate in which the film according to the embodiment of the present disclosure is laminated, but is preferably a laminate having the film according to the embodiment of the present disclosure and a metal layer or a metal wire disposed on at least one surface of the film.
In addition, in the laminate according to the embodiment of the present disclosure, it is more preferable that the laminate has the layer A, the layer B, and the metal layer or the metal wire in this order, the dielectric loss tangent is 0.01 or less, and the surface free energy of the surface of the layer B on the side opposite to the layer A side is 30 mJ/m2 or less.
Furthermore, in the laminate according to the embodiment of the present disclosure, it is more preferable that the laminate has the layer A, the layer B, and a metal layer or a metal wire in this order, the dielectric loss tangent is 0.01 or less, and an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, on a surface of the layer B opposite to a side of the layer A, is higher than an ion intensity derived from a fluorine atom or a silicone structure, which is measured by time-of-flight secondary ion mass spectrometry, inside the layer B.
In addition, the laminate according to the embodiment of the present disclosure preferably has the film according to the embodiment of the present disclosure and a metal layer (for example, gold, silver, copper, iron, or the like) disposed on the surface of the film on the layer B side, and the metal layer is more preferably a copper layer.
The metal layer disposed on the surface of the above-described layer B side is preferably a metal layer disposed on the surface of the above-described layer B.
A method of attaching the film according to the embodiment of the present disclosure to the metal layer is not particularly limited, and a known laminating method can be used.
In a case where the above-described metal layer is the above-described copper layer, a peel strength between the above-described film and the above-described copper layer is preferably 0.5 kN/m or more, more preferably 0.7 kN/m or more, still more preferably 0.7 kN/m to 2.0 kN/m, and particularly preferably 0.9 kN/m to 1.5 kN/m.
In the present disclosure, the cell strength between the film and the metal layer (for example, the copper layer) is measured by the following method.
A peeling test piece with a width of 1.0 cm is produced from the laminate of the film and the metal layer, the film is fixed to a flat plate with double-sided adhesive tape, and the strength (kN/m) in a case of peeling the film off from the metal layer at a rate of 50 mm/min is measured by the 180° method in conformity with JIS C 5016 (1994).
From the viewpoint of reducing transmission loss of high-frequency signal, a surface roughness Rz of the above-described metal layer on the side in contact with the above-described film is preferably less than 1 μm, more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less.
Since it is preferable that the surface roughness Rz of the above-described metal layer is as small as possible, the lower limit value thereof is not particularly set, but may be, for example, 0 or more.
The “surface roughness Rz” in the present disclosure refers to a value expressed in micrometer, which is the total value of the maximum value of height of peak and the maximum value of depth of valley observed on a roughness curve over the reference length.
In the present disclosure, the surface roughness Rz of the metal layer (for example, the copper layer) is measured by the following method.
Using a noncontact surface/layer cross-sectional shape measurement system VertScan (manufactured by MITSUBISHI CHEMICAL SYSTEMS, Inc.), a square of 465.48 μm in length and 620.64 μm in width is measured to create a roughness curve on the surface of the measurement object (metal layer) and create an average line of the roughness curve. A portion corresponding to the reference length is extracted from the roughness curve. The surface roughness Rz of the measurement object is measured by obtaining the total value of the maximum value of height of peak (that is, height from the average line to summit) and the maximum value of depth of valley (that is, depth from the average line to valley bottom) observed in the extracted roughness curve.
The metal layer is preferably a copper layer. As the copper layer, a rolled copper foil formed by a rolling method, an electrolytic copper foil formed by an electrolytic method, a copper foil formed by a sputtering method, or a copper foil formed by a vapor deposition method is preferable.
An average thickness of the metal layer, preferably the copper layer, is not particularly limited, but is preferably 0.1 nm to 30 μm, more preferably 0.1 μm to 20 μm, and still more preferably 1 μm to 18 μm. The copper foil may be copper foil with a carrier formed on a support (carrier) to be peelable. As the carrier, a known carrier can be used. An average thickness of the carrier is not particularly limited, but is preferably 5 μm to 100 μm and more preferably 10 μm to 50 μm.
In addition, from the viewpoint of further exerting the effects of the present disclosure, the above-described metal layer preferably has a known surface treatment layer (for example, a chemical treatment layer) on the surface of the side in contact with the film to ensure adhesion to the resin. In addition, it is preferable that the above-described interactable group is a group corresponding to the functional group of the compound having a functional group, which is contained in the above-described film, such as an amino group and an epoxy group, and a hydroxy group and an epoxy group.
Examples of the interactable group include a group mentioned as the functional group in the above-described compound having a functional group.
Among these, from the viewpoint of adhesiveness and case of performing a treatment, a covalent-bondable group is preferable, an amino group or a hydroxy group is more preferable, and an amino group is particularly preferable.
The metal layer in the laminate according to the embodiment of the present disclosure may be a metal layer having a circuit pattern. It is also preferable that the metal layer in the laminate according to the embodiment of the present disclosure is processed into, for example, a desired circuit pattern by etching to form a flexible printed circuit board. The etching method is not particularly limited, and a known etching method can be used.
Hereinafter, the present disclosure will be described in more detail with reference to examples. The materials, the used amounts, the proportions, the treatment contents, the treatment procedures, and the like described in the following examples can be appropriately changed without departing from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the following specific examples.
In addition, in the present examples, unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass” respectively.
The surface free energy was measured by the method described above.
First, the film was cut in cross section with a microtome or the like, and the layer A or the layer B was specified with an optical microscope. Next, the elastic modulus of the specified layer A or layer B was measured as an indentation clastic modulus using a nanoindentation method. The indentation elastic modulus was measured by using a microhardness tester (product name “DUH-W201”, manufactured by Shimadzu Corporation) to apply a load at a loading rate of 0.28 mN/sec with a Vickers indenter at 160° C., holding a maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/sec.
[Surface Ion Strength of Layer B Derived from Fluorine Atom or Silicone Structure]
The measurement was carried out using TOF-SIMS 5 (Time-of-Flight Secondary Ion Mass Spectrometry, TRIFT V nano TOF) manufactured by ION-TOF GmbH. Bi3+ (25 kV) was used as a primary ion source. The number of irradiated ions was set to 5×1010 ions/cm2 or less.
The detection of the fluorine atom and the silicone structure was carried out for F— and SiC3H9O−, respectively, and the detected value of the corresponding ion in a case where the detected total ion was standardized to 1 was defined as the ion intensity. In addition, regarding the measurement accuracy, F— was set to 0 in a case where the ion strength was less than 0.001. For SiC3H9O−, a value of less than 0.0 was set to 0.
[Surface Ion Intensity Ratio Derived from Fluorine Atom or Silicone]
The surface ion intensity of the layer B measured above was defined as Iout. The surface of the layer B was scraped by 0.5 μm, and the ion intensity of the exposed surface was measured by the same method as described above to obtain an ion intensity Iin inside the layer B. For F— and SiC3H9O−, Iin/out was calculated, and the following evaluation was made.
P1: aromatic polyester amide (liquid crystal polymer) produced by the production method described below
940.9 g (5.0 mol) of 6-hydroxy-2-naphthoic acid, 415.3 g (2.5 mol) of isophthalic acid, 377.9 g (2.5 mol) of acetaminophen, 867.8 g (8.4 mol) of acetic anhydride are put in a reactor comprising a stirring device, a torque meter, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, gas in the reactor is substituted with nitrogen gas, a temperature increases from a room temperature (23° C., the same applies hereinafter) to 140° C. over 60 minutes while stirring under a nitrogen gas flow, and refluxing is performed at 140° C. for three hours.
Next, the temperature increases from 150° C. to 300° C. over five hours while by-produced acetic acid and unreacted acetic anhydride are distilled and is maintained at 300° C. for 30 minutes. Thereafter, a content is taken out from the reactor and is cooled to the room temperature. An obtained solid is ground by a grinder, and powdered aromatic polyester amide Ala is obtained. A flow start temperature of aromatic polyester amide Ala is 193° C. Aromatic polyester amide Ala is fully aromatic polyester amide.
Aromatic polyester amide Ala is subjected to solid-state polymerization by increasing the temperature from the room temperature to 160° C. over two hours and 20 minutes, next increasing the temperature from 160° C. to 180° C. over three hours and 20 minutes, and maintaining the temperature at 180° C. for five hours under a nitrogen atmosphere, and then, is cooled. Next, aromatic polyester amide Ala is pulverized by a pulverizer, and powdered aromatic polyester amide Alb is obtained. A flow start temperature of aromatic polyester amide Alb is 220° C.
Aromatic polyester amide Alb is subjected to solid-state polymerization by increasing the temperature from the room temperature to 180° C. for one hour and 25 minutes, next increasing the temperature from 180° C. to 255° C. over six hours and 40 minutes, and maintaining the temperature at 255° C. for five hours under a nitrogen atmosphere, and then, is cooled, and powdered aromatic polyester amide PI is obtained.
A flow start temperature of aromatic polyester amide PI is 302° C. A melting point of aromatic polyester amide P1 is measured using a differential scanning calorimetry apparatus, and is 311° C. Solubility of aromatic polyester amide PI with respect to N-methylpyrrolidone at 140° C. is equal to or greater than 1% by mass.
PP-1: Liquid crystal polymer particles produced by production method described below
1034.99 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 89.18 g (0.41 mol) of 2,6-naphthalenedicarboxylic acid, 236.06 g (1.42 mol) of terephthalic acid, 341.39 g (1.83 mol) of 4,4-dihydroxybiphenyl, and potassium acetate and magnesium acetate as a catalyst are put in a reactor comprising a stirring device, a torque meter, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser. Gas in the reactor is substituted with nitrogen gas, and then, acetic anhydride (1.08 molar equivalent with respect to a hydroxyl group) is further added. A temperature increases from a room temperature to 150° C. over 15 minutes while stirring under a nitrogen gas flow, and refluxing is performed at 150° C. for two hours.
Next, the temperature increases from 150° C. to 310° C. over five hours while by-produced acetic acid and unreacted acetic anhydride are distilled, and a polymerized substance is taken out and is cooled to the room temperature. An obtained polymerized substance increases in temperature from the room temperature to 295° C. over 14 hours, and is subjected to solid-state polymerization at 295° C. for one hour. After the solid-state polymerization, the temperature was lowered to room temperature over 5 hours, thereby obtaining liquid crystal polymer particles PP-1. The liquid crystal polymer particles PP-1 has a median diameter (D50) of 7 μm, a dielectric loss tangent of 0.0007, and a melting point of 334° C.
P2: a hydrogenated styrene-ethylene-butylene-styrene block copolymer, TAFTEC M1913 manufactured by Asahi Kasci Corporation
PP-2: hydrogenated styrene-ethylene-butylene-styrene block copolymer particles, frozen and pulverized product of TAFTEC M1913 manufactured by Asahi Kasei Corporation (average particle diameter: 5.0 μm (D50))
PP-3: Block copolymer particles of styrene-butadiene, frozen and pulverized product (average particle diameter of 5.0 μm (D50)) of TUFPRENE 912 manufactured by Asahi Kasei Corporation
W1: fluorine-based surfactant polymer W1 produced by the production method described below
W2: fluorine-based surfactant polymer W2 produced by the production method described below
11.7 mmol (5.46 g) of trimethoxy (1H,1H,2H,2H-tridecafluoro-n-octyl) silane, 52.7 mmol (12.24 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 52.5 mmol (12.30 g) of 3-(trimethoxysilyl) propyl acrylate, and 100 g of acetone were placed in a 300 mL three-neck flask comprising a stirring blade, a nitrogen introduction pipe, a cooling pipe, and a thermometer, mixed, and heated to 50° C. under a nitrogen stream. 2.76 g of a 5% potassium carbonate aqueous solution was added dropwise using a dropping funnel over 5 minutes. Subsequently, 18 g of pure water was added dropwise thereto over 20 minutes, and a polycondensation reaction was carried out for 5 hours.
Thereafter, the reaction solution was cooled, 100 g of methyl isobutyl ketone (MIBK) and 100 g of 5% by mass saline were added thereto, and liquid separation washing was performed to extract an organic layer. Further, the organic layer was washed once with 100 g of a 5% by mass saline solution, twice with 100 g of pure water, and then dried by adding magnesium sulfate. After filtering off magnesium sulfate, the solution was concentrated under the conditions of 30 mmHg and 50° C. to obtain a polymer (polyorganosilsesquioxane) represented by Formula (W1), which is a colorless and transparent liquid product, as an MIBK solution having a concentration of solid contents of 52% by mass.
The obtained polymer was analyzed by NMR and IR, and it was confirmed that a target compound was obtained. In addition, the weight-average molecular weight calculated from the GPC measurement was 3,040.
In a 100 mL eggplant flask, 5.0 g of 1,1-dimethoxycyclohexane, 9.0 g of 2-hydroxymethacrylate, 25.0 g of 1H,1H,2H,2H-perfluorooctanol, 0.87 g of pyridinium paratoluenesulfonate, and 30 mL of toluene were weighed, and the mixture was stirred at 40° C. for 1 hour and then stirred at 40° C. for 4 hours under reduced pressure of 100 mmHg. The obtained reaction solution was cooled to room temperature (23° C.) and washed separately with saturated sodium hydrogen carbonate aqueous solution, and the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography, thereby obtaining 8.0 g of a monomer 1 represented by the following formula as a colorless liquid (yield: 40%).
Into a 2,000 mL three-neck flask comprising a stirring blade, a thermometer, and a dropping funnel, 100 g of 2-hydroxyethyl methacrylate and 240 mL of N,N-dimethylacetamide (DMAc) were charged, and cooled in an ice bath. Next, 126.8 g of 3-chloropropionyl chloride was added dropwise thereto, and the mixture was stirred under ice-cooling for 3 hours. The obtained reaction solution was cooled to room temperature and washed separately with 1 mol/L hydrochloric acid in 1,000 mL of ethyl acetate, saturated sodium hydrogen carbonate aqueous solution, and water, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated, thereby obtaining 85 g of a target monomer 2 as a pale yellow liquid (yield: 88%).
2.34 g of the monomer 1, 3.60 g of CYCLOMER M100 (manufactured by Daicel Corporation), 4.05 g of the monomer 2, 18.57 g of methyl ethyl ketone (MEK), and 3.760 g of dimethyl 2,2′-azobis(isobutyrate) (polymerization initiator, manufactured by FUJIFILM Wako Chemicals Corporation) were weighed, and the mixture was stirred at 70° C. for 6 hours.
After the reaction, reprecipitation was carried out using 500 mL of methanol. The obtained solid was dissolved in 15 g of MEK, 5.57 g of triethylamine and 0.01 g of p-methoxyphenol were added thereto, and the mixture was stirred at 60° C. for 4 hours. The reaction solution was allowed to return to room temperature, reprecipitated using 500 mL of methanol, and dissolved in 25 g of MEK, thereby obtaining 5.1 g a polymer W2 (yield: 53%). In the following reaction formula, “M100” represents CYCLOMER M100. In addition, the unit of the content (content ratio) of each constitutional unit in the polymer is “mol %”.
W3: fluorine-based surfactant, MEGAFACE F-444, manufactured by DIC Corporation
W4: silicone-based surfactant, BYK 300, manufactured by BYK-Chemie Japan K.K.
M1: CF-T9DA-SV-18, manufactured by Fukuda Metal Foil & Powder Co., Ltd., average thickness of 18 μm
M2: MT18FL, manufactured by Mitsui Mining & Smelting Co., Ltd., average thickness of 1.5 μm
8 parts of aromatic polyester amide PI was added to 92 parts of N-methylpyrrolidone, and the mixture was stirred at 140° C. for 4 hours under a nitrogen atmosphere to obtain an aromatic polyester amide solution PI (concentration of solid contents: 8% by mass).
An aminophenol type epoxy resin (“jER630” manufactured by Mitsubishi Chemical Corporation, 0.04 parts by mass) was mixed with the aromatic polyester amide solution P1 (10.0 parts by mass) to prepare an undercoat layer coating liquid.
The polymer and the polymer particles shown in Table 1 were mixed in the ratio of parts by mass shown in Table 1, N-methylpyrrolidone was added thereto to adjust the concentration of solid contents to be 25% by mass, and a coating liquid for a layer A was obtained.
The polymer, the polymer particles, and the additive shown in Table 1 were mixed in the ratio of parts by mass shown in Table 1, N-methylpyrrolidone was added thereto to adjust the concentration of solid contents to be 20% by mass, and a coating liquid for a layer B was obtained.
The obtained undercoat layer coating liquid, the coating liquid for the layer A, and the coating liquid for the layer B were fed to a slot die coater equipped with a slide coater, and applied in a three-layer configuration (undercoat layer/layer A/layer B) so that the film thickness was as shown in Table 1 by adjusting the flow rate on the treatment surface of the copper foil shown in Table 2. The solvent was removed from the coating film by drying at 40° C. for 4 hours. The temperature was further raised from room temperature to 300° C. at 1° C./min in a nitrogen atmosphere, and the heat treatment was performed for 2 hours at that temperature to obtain a polymer film having a copper layer (a single-sided copper-clad laminated plate).
The produced films were evaluated by the following methods, and the results are shown in Table 2.
The dielectric loss tangent was measured by a resonance perturbation method at a frequency of 28 GHz. A 28 GHz cavity resonator (CP531 manufactured by KANTO Electronic Application and Development Inc.) is connected to a network analyzer (“E8363B” manufactured by Agilent Technology Co., Ltd.), the test piece is inserted into the cavity resonator, and the dielectric loss tangent of the film is measured from change in resonance frequency before and after insertion for 96 hours under an environment of a temperature of 25° C. and humidity of 60% RH.
20 points in any 10 mm×10 mm area of the produced single-sided copper-clad laminated plate were observed with an optical microscope, and surface defects (aggregation and cissing) having a diameter of 50 μm or more were counted. The evaluation was as follows.
A: The number of surface defects having a diameter of 50 μm or more is less than 0.02 defects/mm2.
B: The number of surface defects having a diameter of 50 μm or more is 0.02 defects/mm2 or more and less than 0.2 defects/mm2.
C: The number of surface defects having a diameter of 50 μm or more is 0.2 defects/mm2 or more.
—Production of Base Material with Wiring Pattern—
A copper foil (product name “CF-T9DA-SV-18”, average thickness of 18 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) and a liquid crystal polymer film (product name “CTQ-50”, average thickness of 50 μm, manufactured by Kuraray Co., Ltd.) as a base material were produced. The copper foil, the base material, and the copper foil were laminated in this order such that the treated surface of the copper foil was in contact with the base material. A double-sided copper-clad laminated plate precursor was obtained by performing a laminating treatment for 1 minute under conditions of 140° C. and a laminating pressure of 0.4 MPa using a laminator (product name “Vacuum Laminator V-130”, manufactured by Nikko-Materials Co., Ltd.). Subsequently, using a thermal compression machine (product name “MP-SNL”, manufactured by Toyo Seiki Seisaku-sho, Ltd.), the obtained double-sided copper-clad laminated plate precursor was thermally compression-bonded for 10 minutes under conditions of 300° C. and 4.5 MPa to prepare a double-sided copper-clad laminated plate.
The copper foils on both surfaces of the above-described double-sided copper-clad laminated plate were roughened, and a dry film resist was bonded thereto. The exposure and development were performed such that the wiring patterns remained, etching was performed, and the dry film was further removed to produce a base material with wiring patterns in which the line/space including the ground line and the three pairs of signal lines on both sides of the base material was 100 μm/100 μm. A length of the signal line was 50 mm, and a width of the signal line was set such that characteristic impedance was 50Ω.
—Production of Base Material with Wiring Pattern—
A copper foil (product name “MT18FL”, average thickness: 1.5 μm, with carrier copper foil (thickness: 18 μm), manufactured by Mitsui Mining & Smelting Co., Ltd.) and a liquid crystal polymer film (product name “CTQ-50”, average thickness: 50 μm, manufactured by Kuraray Co., Ltd.) as a base material were produced. The copper foil, the base material, and the copper foil were laminated in this order such that the treated surface of the copper foil was in contact with the base material. A single-sided copper-clad laminated plate precursor was obtained by performing a laminating treatment for 1 minute under conditions of 140° C. and a laminating pressure of 0.4 MPa using a laminator (product name “Vacuum Laminator V-130”, manufactured by Nikko-Materials Co., Ltd.). Subsequently, using a thermal compression machine (product name “MP-SNL”, manufactured by Toyo Seiki Seisaku-sho, Ltd.), the obtained precursor of the single-sided copper-clad laminated plate was thermally compression-bonded for 10 minutes under the conditions of 300° C. and 4.5 MPa to prepare a single-sided copper-clad laminated plate. The carrier copper foil on the surface of the single-sided copper-clad laminated plate opposite to the base material was peeled off, the exposed 1.5 μm copper foil was roughened, and a dry film resist was bonded thereto. The wiring pattern was exposed and developed, and a plating treatment was performed on a region where the resist pattern was not disposed. Further, the dry film resist was peeled off, and copper exposed in the peeling step was removed by flash etching to produce a base material with wiring patterns having a line/space of 20 μm/20 μm.
The base material with wiring patterns produced above was overlaid on the layer B side of the produced single-sided copper-clad laminated plate, and a hot press was performed for 1 hour under the conditions of 200° C. and 2 MPa to obtain a wiring board.
In the obtained wiring board, wiring patterns (a ground line and a signal line) were buried, and in a case where the base material A with wiring patterns was used, the thickness of the wiring patterns was 18 μm, and in a case where the base material B with wiring patterns was used, the thickness of the wiring patterns was 12 μm.
The wiring board was cut in a thickness direction with a microtome, and the cross sections of 100 wiring patterns were observed with a scanning electron microscope (SEM). The number of voids of 1 μm or more generated between the resin layer and the wiring pattern was counted, and the following evaluation was performed.
A copper foil (product name “CF-T9DA-SV-18”, average thickness: 18 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) was prepared. The copper foil and the single-sided copper-clad laminated plate were laminated in this order so that the untreated surface of the copper foil was in contact with the layer B side of the produced single-sided copper-clad laminated plate. A double-sided copper-clad laminated plate precursor was obtained by performing a laminating treatment for 1 minute under conditions of 140° C. and a laminating pressure of 0.4 MPa using a laminator (product name “Vacuum Laminator V-130”, manufactured by Nikko-Materials Co., Ltd.). Subsequently, using a thermal compression machine (product name “MP-SNL”, manufactured by Toyo Seiki Seisaku-sho, Ltd.), the obtained double-sided copper-clad laminated plate precursor was thermally compression-bonded for 60 minutes under conditions of 200° C. and 4 MPa to prepare a double-sided copper-clad laminated plate.
A peeling test piece having a width of 1.0 cm was produced from the obtained double-sided copper-clad laminated plate, the copper foil side subjected to the thermal compression bonding was fixed to a flat plate with a double-sided adhesive tape, and a strength (kN/m) in a case where the single-sided copper-clad laminated plate was peeled off from the metal layer at a rate of 50 mm/min was measured according to the 90° method in conformity with JIS C 5016 (1994).
From the results shown in Tables 1 and 2, the films of Examples 1 to 12, which are the films according to the embodiment of the present disclosure, have excellent surface defect suppression properties as compared with the film of Comparative Example 1.
In addition, from the results shown in Tables 1 and 2, the films of Examples 1 to 12 which are the films according to the embodiment of the present disclosure have a low dielectric loss tangent, and have excellent void suppression properties in the wiring line and adhesiveness to the metal.
The disclosure of JP2022-138488 filed on Aug. 31, 2022 is incorporated in the present specification by reference in its entirety.
All documents, patent applications, and technical standards described in the present specification are herein incorporated by reference to the same extent that individual documents, patent applications, and technical standards have been specifically and individually indicated to be incorporated by reference, respectively.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-138488 | Aug 2022 | JP | national |
This application is a continuation application of International Application No. PCT/JP2023/031834, filed Aug. 31, 2023, the disclosure of which is incorporated herein by reference in its entirety. Further, this application claims priority from Japanese Patent Application No. 2022-138488, filed Aug. 31, 2022, the disclosure of which is incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/031834 | Aug 2023 | WO |
| Child | 19052296 | US |
