JP2019176958A - Base material, printed wiring board, biological contact device, biological implant device and artificial organ - Google Patents

Abstract

To provide a base material that has high affinity with biological tissue, has excellent followability to body motion and excellent durability, hardly absorbs water, and can be reduced in size, and provide a printed wiring board, biological contact device, biological implant device and artificial organ.SOLUTION: The present invention provides a base material 12 used for a biological contact device, biological implant device or artificial organ, the base material 12 having a fluororesin layer 20 containing fluororesin, and the fluororesin layer 20 having a breaking elongation at 200°C of 20-400%.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a substrate and a printed wiring board used for a biological contact device, a biological implant device or an artificial organ, and a biological contact device, a biological implant device and an artificial organ.

  Since fluororesin has a high affinity with living tissue, it has been proposed to be used as a material for printed wiring boards provided in wearable or implantable biological information measuring devices and as a material for artificial organ substrates. (Patent Documents 1 and 2).

JP-A-2015-122448 Japanese Patent Laid-Open No. 4-336072

Substrates and printed wiring boards used for biological contact devices, biological implant devices, or artificial organs have the flexibility to follow the movement of the body (followability), and repeatedly expand and contract and follow the movement of the body. However, it is required to be difficult to break (durability), not to cause a problem due to water absorption, to be able to be downsized in order to suppress a sense of incongruity when mounted or embedded.
However, the base materials and printed wiring boards described in Patent Documents 1 and 2 are insufficiently flexible and may not sufficiently follow the movement of the body.

  The present invention provides a substrate, printed wiring board, biocontact device, and bioimplantable device that have high affinity with a living tissue, excellent followability and durability with respect to body movement, are difficult to absorb water, and can be reduced in size. And providing an artificial organ.

The present invention has the following aspects.
<1> A substrate used for a biological contact device, a biological implant device or an artificial organ, wherein the substrate has a fluororesin layer containing a fluororesin, and the fluororesin layer has an elongation at break at 200 ° C. A substrate that is 20-400%.
<2> The fluorine resin having a melting point of 260 ° C. or higher and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group The base material according to <1>, which is a resin.
<3> The substrate according to <1> or <2>, wherein at least one surface of the fluororesin layer is treated with a silane coupling agent.
<4> The base material according to any one of <1> to <3>, further including a metal layer in contact with the fluororesin layer.
<5> The base material according to <4>, wherein the peel strength between the fluororesin layer and the metal layer is 5 N / cm or more.
<6> The base material according to <4> or <5>, further including any one or both of a heat resistant resin layer and a fiber reinforced resin layer in contact with the fluororesin layer.
<7> The substrate according to <6>, wherein the peel strength between the fluororesin layer and the heat resistant resin layer or the fiber reinforced resin layer is 5 N / cm or more.
<8> A printed wiring board obtained by processing the metal layer in the base material according to any one of <4> to <7> into a conductor circuit.
<9> A biological contact device comprising the substrate according to any one of <1> to <7> or the printed wiring board according to <8>.
<10> A living body implantable device comprising the substrate according to any one of <1> to <7> or the printed wiring board according to <8>.
<11> An artificial organ comprising the substrate according to any one of <1> to <7> or the printed wiring board according to <8>.

  The substrate, printed wiring board, living body contact device, living body implantable device and artificial organ of the present invention have high affinity with living tissue, excellent followability to body movement and durability, hardly absorb water, and are small in size. Is possible.

It is sectional drawing which shows an example of the base material of this invention. It is sectional drawing which shows the other example of the base material of this invention. It is sectional drawing which shows the other example of the base material of this invention. It is sectional drawing which shows an example of the printed wiring board of this invention. It is sectional drawing which shows the other example of the printed wiring board of this invention.

The following terms have the following meanings:
“Elongation at break” is a value measured according to JIS K 6251: 2010 (corresponding international standard ISO 37: 2005).
The “peel strength” is a value measured as follows. A rectangular test piece having a length of 100 mm and a width of 10 mm is cut out from the substrate. The fluororesin layer and the metal layer, the heat resistant resin layer, or the fiber reinforced resin layer are peeled from one end in the length direction of the test piece to a position of 50 mm. With a position of 50 mm from one end in the length direction of the test piece as the center, the tensile tester is used to peel 90 degrees at a tensile speed of 50 mm / min, and the maximum load is taken as the peel strength (N / cm).
“Melt moldable” means exhibiting melt fluidity.
“Showing melt fluidity” means that there is a temperature at which the MFR is 0.01 to 1000 g / 10 min at a temperature higher than the melting point of the resin by 20 ° C. or more under the condition of a load of 49 N.
The “melting point” is a temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
“MFR” is a melt mass flow rate defined in JIS K 7210-1: 2014 (corresponding international standard ISO 1133-1: 2011).
"Relative permittivity" is a test environment in which the temperature is kept within a range of 23 ° C ± 2 ° C and the relative humidity within a range of 50% ± 5% RH according to a transformer bridge method in accordance with ASTM D 150. It is the value calculated | required at 1 MHz using the dielectric breakdown test apparatus (the Yamayo Tester company make, YSY-243-100RHO). In the high frequency band, this is a value measured at a frequency of 20 GHz in an environment within the range of 23 ° C. ± 2 ° C. and 50 ± 5% RH by the SPDR (split post dielectric resonator) method. Hereinafter, the relative permittivity measured at 1 MHz is referred to as “relative permittivity (1 MHz)”, and the relative permittivity measured at 20 GHz is referred to as “relative permittivity (20 GHz)”.
“D50 of resin powder” is a volume-based cumulative 50% diameter determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained by setting the total volume of the group of particles as 100%, and the particle diameter is the point at which the cumulative volume is 50% on the cumulative curve.
“D90 of resin powder” is a volume-based cumulative 90% diameter determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained by setting the total volume of the group of particles as 100%, and the particle diameter is the point at which the cumulative volume is 90% on the cumulative curve.
“Arithmetic average roughness Ra” is an arithmetic average roughness measured based on JIS B 0601: 2013 (corresponding international standard ISO 4287: 1997, Amd. 1: 2009). The reference length lr (cutoff value λc) for the roughness curve when calculating the arithmetic average roughness Ra is 0.8 mm.
“Ra (AFM)” is the arithmetic average roughness Ra as measured with an atomic force microscope (AFM).
“Rz (AFM)” is the maximum height Rz when measured by AFM.
Ra (AFM) and Rz (AFM) using the Oxford Instruments Inc. of AFM, measured for the surface of the 1 [mu] m ² range under the following measurement conditions.
Probe: AC160TS-C3 (tip R <7 nm, spring constant 26 N / m), measurement mode: AC-Air, Scan Rate: 1 Hz.
The “wetting tension” is a value measured according to JIS K 6768: 1999 (corresponding international standard ISO 8296: 1987).
“Heat resistant resin” means a high molecular compound having a melting point of 280 ° C. or higher, or a high molecular compound having a maximum continuous use temperature defined by JIS C 4003: 2010 (IEC 60085: 2007) of 121 ° C. or higher.
The “carbonyl group-containing group” means a group having a carbonyl group (—C (═O) —) in the structure.
The “acid anhydride residue” means a group represented by —C (═O) —O—C (═O) —.
The “etheric oxygen atom” means an oxygen atom that exists between carbon and carbon atoms.
“Unit based on monomer” is a general term for an atomic group directly formed by polymerizing one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group. In the present specification, a unit based on a monomer is also simply referred to as a monomer unit.
“Monomer” means a compound having a polymerizable carbon-carbon double bond.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“˜” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
The dimensional ratios in FIGS. 1 to 5 are different from actual ones for convenience of explanation.

<Base material>
The base material of the present invention is a material used for a part or the whole of a biological contact device, a biological implant device, or an artificial organ.
The base material of the present invention has a fluororesin layer.
The base material of the present invention may further have a metal layer in contact with the fluororesin layer.
The base material of the present invention may further have one or both of a heat resistant resin layer and a fiber reinforced resin layer in contact with the fluororesin layer.
In the range which does not impair the effect of this invention, the base material of this invention may further have layers other than a fluororesin layer, a metal layer, a heat resistant resin layer, and a fiber reinforced resin layer as needed.

The base material of the present invention may be a single-layer base material composed only of a fluororesin layer, or may be a laminated base material having a fluororesin layer and a layer other than the fluororesin layer.
As the layer structure of the laminated substrate, fluororesin layer / metal layer, metal layer / fluororesin layer / metal layer, fluororesin layer / heat resistant resin layer or fiber reinforced resin layer, heat resistant resin layer or fiber reinforced resin layer / Examples thereof include fluorine resin layer / metal layer, metal layer / fluorine resin layer / heat resistant resin layer, fiber reinforced resin layer / fluorine resin layer / metal layer, and the like. “Metal layer / resin layer” means that a metal layer and a resin layer are laminated in this order, and the other layer configurations are the same.

FIG. 1 is a cross-sectional view showing an example of the substrate of the present invention.
The base material 11 is a single-layer base material made only of the fluororesin layer 20.

FIG. 2 is a cross-sectional view showing another example of the substrate of the present invention.
The substrate 12 includes a fluororesin layer 20 and a metal layer 22 that is in contact with the first surface of the fluororesin layer 20.

FIG. 3 is a cross-sectional view showing another example of the substrate of the present invention.
The base material 13 includes a fluororesin layer 20, a metal layer 22 in contact with the first surface of the fluororesin layer 20, and a heat resistant resin layer or a fiber reinforced resin layer 24 in contact with the second surface of the fluororesin layer 20. Have.

  The peel strength between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer in the substrate of the present invention is preferably 5 N / cm or more, more preferably 8 N / cm or more, and 10 N / cm or more. Is more preferable. If the peel strength is equal to or greater than the lower limit of the above range, the adhesiveness between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer is excellent, and as a result, even if it is repeatedly expanded and contracted, it is delaminated. Difficult, more durable against body movements. The higher the peel strength, the better, and the upper limit is not limited.

(Fluorine resin layer)
The fluororesin layer contains a fluororesin.
The fluororesin layer may contain an inorganic filler, a resin other than the fluororesin, an additive, and the like as necessary within a range not impairing the effects of the present invention.
The proportion of the fluororesin is preferably 80% by mass or more and more preferably 90% by mass or more in the fluororesin layer. The upper limit of the ratio of the fluororesin is 100% by mass.

  The elongation at break of the fluororesin layer at 200 ° C. is 20 to 400%, preferably 40 to 350%, more preferably 50 to 300%. If elongation at the time of cutting is equal to or greater than the lower limit of the above range, the followability of the substrate and the printed wiring board with respect to body movement is excellent. If the elongation at the time of cutting is below the upper limit of the above range, the fluororesin layer will not be stretched too much when the body is moved, and the displacement between the conductor circuit and the fluororesin layer in the printed wiring board is suppressed, and the movement of the body Excellent durability of the base material and printed wiring board. In addition, problems such as short-circuiting due to movement of the conductor circuit can be suppressed.

Since the fluororesin layer contains a fluororesin having a low relative dielectric constant and dielectric loss tangent, the electrical characteristics are excellent even when it is thin. Therefore, the base material and printed wiring board having the fluororesin layer can be downsized (thinned).
The thickness of the fluororesin layer is preferably from 0.1 to 500 μm, more preferably from 3 to 200 μm, still more preferably from 5 to 100 μm. When the thickness of the fluororesin layer is equal to or more than the lower limit, the transmission characteristics as a printed wiring board are excellent. If the thickness of the fluororesin layer is not more than the above upper limit value, the substrate and the printed wiring board can be further miniaturized.

  The relative dielectric constant (1 MHz) of the fluororesin layer is preferably 2.0 to 3.5, more preferably 2.0 to 3.0. If the relative dielectric constant (1 MHz) is not more than the upper limit of the above range, a substrate can be suitably used for a printed wiring board or the like for which a low dielectric constant is required. When the relative dielectric constant (1 MHz) of the fluororesin layer is equal to or higher than the lower limit of the above range, both the electrical characteristics and adhesiveness of the fluororesin layer are excellent.

  The arithmetic average roughness Ra of the surface of the fluororesin layer is less than the thickness of the fluororesin layer, and is preferably 2.0 to 30 μm, more preferably 2.0 to 15 μm, and further preferably 2.1 to 12 μm. 2.1 to 10 μm is particularly preferable, and 2.2 to 8 μm is most preferable. If the arithmetic average roughness Ra is not less than the lower limit of the above range, the adhesiveness between the fluororesin layer and the metal layer, the heat resistant resin layer or the fiber reinforced resin layer is excellent, and as a result, even if it is repeatedly stretched or bent Delamination is difficult and durability against body movement is even better. If arithmetic average roughness Ra is below the upper limit of the said range, a metal layer, a heat resistant resin layer, or a fiber reinforced resin layer can be laminated | stacked, without a through-hole being formed in a fluororesin layer.

  Ra (AFM) on the surface of the fluororesin layer is preferably 3.0 nm or more, and more preferably 12 nm or more. If Ra (AFM) is not less than the lower limit of the above range, the adhesiveness between the fluororesin layer and the metal layer, the heat-resistant resin layer or the fiber reinforced resin layer is excellent, and as a result, even when repeatedly stretched or bent, the interlayer It is difficult to peel off and is more durable against body movement. Ra (AFM) is preferably 1 μm or less.

  The wetting tension of the surface of the fluororesin layer is preferably 30 mN / m or more, more preferably 30 to 70 mN / m, and even more preferably 40 to 65 mN / m. If the wetting tension is not less than the lower limit of the above range, the adhesion between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer is excellent, and as a result, it is difficult to delaminate even when repeatedly stretched or bent. , Durability against body movement is even better.

  The arithmetic average roughness Ra, Ra (AFM) and wetting tension of the surface of the fluororesin layer can be adjusted by, for example, plasma-treating the surface of the fluororesin layer. The plasma processing will be described later.

As the fluororesin, a fluororesin that can be melt-molded is preferable from the viewpoint of easy production of a substrate and a printed wiring board.
Melt-moldable fluororesins include tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoro Examples thereof include ethylene, ethylene-chlorotrifluoroethylene copolymer, fluoropolymer A described later, and modified polytetrafluoroethylene. Also, polytetrafluoroethylene may be used as long as it exhibits melt fluidity.

The modified polytetrafluoroethylene is a copolymer of (i) tetrafluoroethylene (hereinafter also referred to as “TFE”) and a trace amount of CH ₂ ═CH (CF ₂ ) ₄ F or CF ₂ ═CFOCF _3. (Ii) a copolymer obtained by further copolymerizing a very small amount of an adhesive functional group-containing monomer with (i), (iii) a copolymer obtained by copolymerizing TFE and a very small amount of an adhesive functional group-containing monomer, Examples include (iv) those obtained by introducing an adhesive functional group into polytetrafluoroethylene by plasma treatment or the like, and (v) those obtained by introducing an adhesive functional group into the above (i) by plasma treatment or the like.
When a fluororesin that cannot be melt-molded, for example, unmodified polytetrafluoroethylene that does not exhibit melt fluidity, is used in place of the melt-moldable fluororesin, a mechanical pulverization process is used when producing the resin powder described below. Since polytetrafluoroethylene fibrillates, it is difficult to obtain resin powder.

The MFR of the fluororesin at a temperature higher than the melting point of the fluororesin by 20 ° C. or more is preferably 0.01 to 1000 g / 10 minutes, more preferably 0.1 to 1000 g / 10 minutes, and 0.5 to 100 g / 10 minutes. More preferably, 1 to 30 g / 10 min is particularly preferable, and 5 to 20 g / 10 min is most preferable. If MFR is not less than the lower limit of the above range, it is easy to produce a substrate and a printed wiring board. If MFR is below the upper limit of the said range, it will be excellent in the mechanical strength of a fluororesin layer.
MFR is a measure of the molecular weight of the fluororesin. When the MFR is large, the molecular weight is small, and when the MFR is small, the molecular weight is large.
The MFR of the fluororesin can be adjusted depending on the production conditions of the fluororesin. For example, if the polymerization time is shortened during polymerization of the monomer, the MFR tends to increase.

The melting point of the fluororesin is preferably 170 ° C. or higher, more preferably 200 to 380 ° C., further preferably 260 to 320 ° C., still more preferably 280 to 320 ° C., particularly preferably 295 to 315 ° C., and 295 to 310 ° C. Most preferred. When the melting point of the fluororesin is at least the lower limit of the above range, the heat resistance of the fluororesin layer is excellent. When the melting point of the fluororesin is not more than the upper limit of the above range, the melt moldability of the fluororesin is excellent.
The melting point of the fluororesin can be adjusted by the type and ratio of units constituting the fluororesin, the molecular weight of the fluororesin, and the like. For example, the melting point tends to increase as the proportion of TFE units increases.

The relative dielectric constant (1 MHz) of the fluororesin is preferably 2.5 or less, more preferably 2.4 or less, and particularly preferably 2.0 to 2.4. The lower the relative dielectric constant (1 MHz) of the fluororesin, the better the electrical characteristics of the fluororesin layer, and the more excellent the transmission characteristics of a printed wiring board using a substrate having a fluororesin layer. The lower limit value of the relative dielectric constant (1 MHz) is usually 2.0.
The relative dielectric constant (20 GHz) of the fluororesin is preferably 2.5 or less, more preferably 2.4 or less, and particularly preferably 2.0 to 2.4. The lower the relative dielectric constant (20 GHz) of the fluororesin, the more excellent the electrical characteristics of the fluororesin layer, and the better the transmission efficiency of a printed wiring board using a substrate having a fluororesin layer.
The relative dielectric constant of the fluororesin can be adjusted by the ratio of TFE units.

  As the fluororesin, at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group (hereinafter also referred to as “adhesive functional group”). What has is preferable. If the fluororesin has an adhesive functional group, the affinity between the fluororesin layer and the living tissue is further increased. In addition, it has excellent adhesion between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer, and as a result, it is difficult to delaminate even when repeatedly stretched or bent, and it is more durable against body movement. .

  As a fluororesin having an adhesive functional group, the fluororesin has a lower relative dielectric constant and dielectric loss tangent, and further has excellent heat resistance, chemical resistance, etc. The fluorine-containing polymer A having a group is preferable.

The adhesive functional group may be contained in the unit in the fluoropolymer A. In that case, the unit having the adhesive functional group may be a unit having a fluorine atom, or a unit having no fluorine atom. It may be. Hereinafter, a unit having an adhesive functional group is also referred to as an “adhesive functional group-containing unit”. As the adhesive functional group-containing unit, a unit having no fluorine atom is preferable.
The adhesive functional group may be contained in the terminal group of the main chain of the fluoropolymer A. In that case, the fluoropolymer A may have an adhesive functional group-containing unit, and It does not have to be. A terminal group having an adhesive functional group is a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and has an adhesive functional group, or generates an adhesive functional group during a polymer formation reaction. By using one or both of an initiator and a chain transfer agent, a terminal group having an adhesive functional group is formed. Also, an adhesive functional group can be introduced into the end group after the polymer is formed. The adhesive functional group contained in the terminal group is preferably an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue, or a hydroxy group.

  As the fluoropolymer A, a copolymer having an adhesive functional group-containing unit and a TFE unit is preferable. In that case, the fluoropolymer A may further have units other than the adhesive functional group-containing unit and the TFE unit, if necessary. As units other than the adhesive functional group-containing unit and the TFE unit, perfluoro units such as a PAVE unit and an HFP unit described later are preferable.

As the adhesive functional group in the adhesive functional group-containing unit, the mechanical grindability of the fluoropolymer A, and the adhesiveness between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer are excellent. A carbonyl group-containing group is preferred.
Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, carbonate group, carboxy group, haloformyl group, alkoxycarbonyl group, acid anhydride residue, polyfluoroalkoxycarbonyl group, fatty acid residue, etc. Is mentioned. As the carbonyl group-containing group, the carbon atom of the hydrocarbon group from the viewpoint of excellent mechanical grindability of the fluoropolymer A, and excellent adhesion between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer. At least one selected from the group consisting of a group having a carbonyl group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group and an acid anhydride residue is preferred, and either a carboxy group or an acid anhydride residue One or both are more preferred.

Examples of the hydrocarbon group in the group having a carbonyl group between carbon atoms of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms. The number of carbon atoms of the alkylene group is the number of carbons in a state in which the carbon constituting the carbonyl group is not included. The alkylene group may be linear or branched.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
The alkoxy group in the alkoxycarbonyl group may be linear or branched, and is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably a methoxy group or an ethoxy group.

As the adhesive functional group-containing unit, a unit based on an adhesive functional group-containing monomer is preferable.
The adhesive functional group-containing monomer may have one or two or more adhesive functional groups. In the case of having two or more adhesive functional groups, the two or more adhesive functional groups may be the same or different from each other.
As the adhesive functional group-containing monomer, a compound having one adhesive functional group and one polymerizable carbon-carbon double bond is preferable.

  Examples of the adhesive functional group-containing monomer include a monomer having a carbonyl group-containing group, a hydroxy group-containing monomer, an epoxy group-containing monomer, and an isocyanate group-containing monomer. As the adhesive functional group-containing monomer, a carbonyl group can be used from the viewpoint of excellent mechanical grindability of the fluoropolymer A, and adhesion between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer. Monomers having a containing group are preferred.

As a monomer having a carbonyl group-containing group, an acid anhydride residue-containing cyclic monomer, a carboxy group-containing monomer, a vinyl ester, (meth) acrylate, CF ₂ = CFOR ^f1 C (O) OX ¹ ( However, R ^f1 is a group having an etheric oxygen atom between carbon atoms of the perfluoroalkylene group perfluoroalkylene group, or a C2-10 having 1 to 10 carbon atoms, X ¹ is a hydrogen atom or a carbon atoms 1 to 3 alkyl groups).

Examples of the acid anhydride residue-containing cyclic monomer include unsaturated dicarboxylic acid anhydrides. Examples of the unsaturated dicarboxylic acid anhydride include itaconic anhydride (hereinafter also referred to as “IAH”), citraconic anhydride (hereinafter also referred to as “CAH”), 5-norbornene-2,3-dicarboxylic acid anhydride ( Another name: hymic anhydride, hereinafter also referred to as “NAH”), and maleic anhydride.
Carboxy group-containing monomers include unsaturated dicarboxylic acids (itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.), unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, etc.), etc. Is mentioned.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate and the like.
Examples of (meth) acrylates include (polyfluoroalkyl) acrylate and (polyfluoroalkyl) methacrylate.

  The monomer having a carbonyl group-containing group is excellent in the thermal stability of the fluororesin layer, and is more excellent in adhesion between the fluororesin layer and the metal layer, heat resistant resin layer or fiber reinforced resin layer. An anhydride residue-containing cyclic monomer is preferred, and at least one selected from the group consisting of IAH, CAH and NAH is more preferred. When at least one selected from the group consisting of IAH, CAH and NAH is used, acid anhydride can be used without using a special polymerization method required when maleic anhydride is used (see JP-A-11-19312). Fluoropolymer A having a residue can be easily produced. As the monomer having a carbonyl group-containing group, NAH is particularly preferable because the adhesion between the fluororesin layer and the metal layer, the heat resistant resin layer, or the fiber reinforced resin layer is further improved.

Hydroxy group-containing monomers include hydroxy group-containing vinyl esters, hydroxy group-containing vinyl ethers, hydroxy group-containing allyl ethers, hydroxy group-containing (meth) acrylates (such as 2-hydroxyethyl (meth) acrylate), and hydroxyethyl crotonic acid ( And 2-hydroxyethyl crotonic acid) and allyl alcohol.
Examples of the epoxy group-containing monomer include unsaturated glycidyl ether (eg, allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether), unsaturated glycidyl ester (eg, glycidyl acrylate, glycidyl methacrylate), and the like.
Examples of the isocyanate group-containing monomer include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, and the like. Is mentioned.
An adhesive functional group containing monomer may be used individually by 1 type, and may use 2 or more types together.

  As other units other than the adhesive functional group-containing unit and the TFE unit, a unit based on perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”), hexafluoropropylene (hereinafter also referred to as “HFP”). Examples thereof include units based on units based on units, adhesive functional group-containing monomers, monomers other than TFE, PAVE and HFP (hereinafter also referred to as “other monomers”).

As PAVE, CF ₂ = CFOR ^f2 (where R ^f2 is a group having an etheric oxygen atom between carbon atoms of a C 1-10 perfluoroalkyl group or a C 2-10 perfluoroalkyl group. .).
The perfluoroalkyl group for R ^f2 may be linear or branched. R ^f2 preferably has 1 to 3 carbon atoms.
As CF ₂ = CFOR ^f2 , CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ ═CFO (CF ₂ ) ₈ F and the like, and PPVE is preferable.
PAVE may be used individually by 1 type and may use 2 or more types together.

  Other monomers include other fluorine-containing monomers (excluding adhesive functional group-containing monomers, TFE, PAVE and HFP), other non-fluorinated monomers (however, adhesiveness) The functional group-containing monomer is excluded.

Other fluorine-containing monomers include fluoroolefins excluding TFE and HFP (vinyl fluoride, vinylidene fluoride (hereinafter also referred to as “VdF”), trifluoroethylene, chlorotrifluoroethylene (hereinafter “CTFE”). and also referred.), ^{_{etc.), CF 2 = CFOR f3 SO}} 2 X 3 ( provided ^{that, R f3} is a perfluoroalkylene group having 1 to 10 carbon atoms, or ethereal between carbon atoms of the perfluoroalkylene group having 2 to 10 carbon atoms A group having an oxygen atom, and X ³ is a halogen atom or a hydroxy group.), CF ₂ ═CF (CF ₂ ) _s OCF═CF ₂ (wherein s is 1 or 2), CH ₂ = ^{_{CX 4 (CF 2) t X}} 5 ( however, ^{X 4} is a hydrogen atom or a fluorine atom, t is an integer from 2 to 10, ^{X 5} is a hydrogen atom or a fluoride An atom.), Perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like. Another fluorine-containing monomer may be used individually by 1 type, and may use 2 or more types together.

Other fluorinated monomers, VdF, CTFE and ^{_{CH 2 = CX 4 (CF 2}} ) at least one selected from the group consisting of t ^{X 5} are preferred.
As CH ₂ = CX ⁴ (CF ₂ ) _t X ⁵ , CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ ═CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H and the like, and CH ₂ ═CH (CF ₂ ) ₄ F and CH ₂ ═CH (CF ₂ ) ₂ F are preferable.

Other non-fluorinated monomers include olefins having 3 or less carbon atoms (ethylene, propylene, etc.), ethylene and propylene are preferred, and ethylene is particularly preferred. Other non-fluorinated monomers may be used alone or in combination of two or more.
As another monomer, another fluorine-containing monomer and another non-fluorine-containing monomer may be used in combination.

As the fluorine-containing polymer A, the fluorine-containing polymer A1 and the fluorine-containing polymer A2 are preferable, and the fluorine-containing polymer A1 is particularly preferable from the viewpoint of excellent heat resistance of the fluorine resin layer.
Fluoropolymer A1: A copolymer having an adhesive functional group-containing unit, a TFE unit, and a PAVE unit.
Fluoropolymer A2: a copolymer having an adhesive functional group-containing unit, a TFE unit, and an HFP unit.

  The fluoropolymer A1 may further have either one or both of an HFP unit and another monomer unit as necessary. That is, the fluorinated polymer A1 may be a copolymer comprising an adhesive functional group-containing unit, a TFE unit, and a PAVE unit. From the adhesive functional group-containing unit, the TFE unit, the PAVE unit, and the HFP unit. A copolymer comprising an adhesive functional group-containing unit, a TFE unit, a PAVE unit, and another monomer unit, or an adhesive functional group-containing unit and a TFE unit. And a copolymer comprising PAVE units, HFP units, and other monomer units.

As the fluorinated polymer A1, a carbonyl group-containing group is obtained because the mechanical grindability of the fluorinated polymer A1 and the adhesion between the fluororesin layer and the metal layer, the heat-resistant resin layer or the fiber reinforced resin layer are further improved. A copolymer having a unit based on a monomer having a TFE unit and a PAVE unit is preferred, and a copolymer having a unit based on an acid anhydride residue-containing cyclic monomer, a TFE unit and a PAVE unit is particularly preferred. preferable. Preferable specific examples of the fluoropolymer A1 include the following.
A copolymer having TFE units, PPVE units and NAH units;
A copolymer having TFE units, PPVE units, and IAH units;
A copolymer having TFE units, PPVE units, and CAH units.

  The fluoropolymer A1 may have an adhesive functional group as a terminal group. The adhesive functional group can be introduced by appropriately selecting a polymerization initiator, a chain transfer agent and the like used in the production of the fluoropolymer A1.

  The proportion of the adhesive functional group-containing unit in the fluoropolymer A1 is preferably 0.01 to 3 mol%, more preferably 0.03 to 2 mol%, of all units constituting the fluoropolymer A1. 0.05-1 mol% is more preferable. If the ratio of the adhesive functional group-containing unit is not less than the lower limit of the above range, the adhesion between the fluororesin layer and the metal layer, the heat resistant resin layer or the fiber reinforced resin layer is further improved. If the ratio of the adhesive functional group-containing unit is not more than the upper limit of the above range, the heat resistance and color of the resin powder are excellent.

  The ratio of the TFE unit in the fluoropolymer A1 is preferably 90 to 99.89 mol%, more preferably 95 to 99.47 mol%, and more preferably 96 to 98.% of all units constituting the fluoropolymer A1. 95 mol% is more preferable. If the ratio of the TFE unit is at least the lower limit of the above range, the relative permittivity and dielectric loss tangent of the fluoropolymer A1 are further reduced, and the fluoropolymer A1 is excellent in heat resistance, chemical resistance, and the like. When the proportion of TFE units is not more than the upper limit of the above range, the fluoropolymer A1 is excellent in melt moldability, stress crack resistance, and the like.

The proportion of PAVE units in the fluorinated polymer A1 is preferably from 0.1 to 9.99 mol%, more preferably from 0.5 to 9.97 mol%, based on the total units constituting the fluorinated polymer A1. 1-9.95 mol% is more preferable. When the ratio of the PAVE unit is within the above range, the melt-formability of the fluoropolymer A1 is excellent.
The total of the adhesive functional group-containing units, TFE units and PAVE units in the fluoropolymer A1 is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more. The upper limit of the total of the adhesive functional group-containing unit, the TFE unit and the PAVE unit is 100 mol%.

  The fluorine-containing polymer A2 may further have one or both of a PAVE unit and another monomer unit as necessary. That is, the fluorinated polymer A2 may be a copolymer comprising an adhesive functional group-containing unit, a TFE unit, and an HFP unit. From the adhesive functional group-containing unit, the TFE unit, the HFP unit, and the PAVE unit, A copolymer comprising an adhesive functional group-containing unit, a TFE unit, an HFP unit, and another monomer unit, and an adhesive functional group-containing unit and a TFE unit. And a copolymer comprising HFP units, PAVE units, and other monomer units.

As the fluorinated polymer A2, a carbonyl group-containing group is obtained from the point that the mechanical grindability of the fluorinated polymer A2 and the adhesion between the fluororesin layer and the metal layer, the heat resistant resin layer or the fiber reinforced resin layer are further improved. A copolymer having a unit based on a monomer having a monomer, a TFE unit and a HFP unit is preferred, and a copolymer having a unit based on an acid anhydride residue-containing cyclic monomer, a TFE unit and a HFP unit is particularly preferred. preferable. Preferable specific examples of the fluoropolymer A2 include the following.
A copolymer having TFE units, HFP units and NAH units;
A copolymer having TFE units, HFP units and IAH units;
A copolymer having TFE units, HFP units, and CAH units.
The fluoropolymer A2 may have a terminal group having an adhesive functional group, like the fluoropolymer A1.

  The proportion of the adhesive functional group-containing unit in the fluorinated polymer A2 is preferably 0.01 to 3 mol%, more preferably 0.02 to 2 mol%, of all units constituting the fluorinated polymer A2. 0.05-1.5 mol% is more preferable. If the ratio of the adhesive functional group-containing unit is not less than the lower limit of the above range, the adhesion between the fluororesin layer and the metal layer, the heat resistant resin layer or the fiber reinforced resin layer is further improved. If the ratio of the adhesive functional group-containing unit is not more than the upper limit of the above range, the heat resistance and color of the resin powder are excellent.

  The proportion of TFE units in the fluorinated polymer A2 is preferably 90 to 99.89 mol%, more preferably 91 to 98 mol%, and more preferably 92 to 96 mol% of all units constituting the fluorinated polymer A2. Further preferred. When the ratio of the TFE unit is at least the lower limit of the above range, the relative permittivity and dielectric loss tangent of the fluoropolymer A2 are further reduced, and the fluoropolymer A2 is excellent in heat resistance, chemical resistance, and the like. When the proportion of TFE units is not more than the upper limit of the above range, the fluoropolymer A2 is excellent in melt moldability, stress crack resistance, and the like.

The proportion of HFP units in the fluorinated polymer A2 is preferably from 0.1 to 9.99 mol%, more preferably from 1 to 9 mol%, and more preferably from 2 to 8 mol, among all the units constituting the fluorinated polymer A2. % Is more preferable. When the ratio of the HFP unit is within the above range, the melt-formability of the fluoropolymer A2 is excellent.
The total of the adhesive functional group-containing unit, TFE unit and HFP unit in the fluoropolymer A2 is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more. The upper limit of the total of the adhesive functional group-containing unit, TFE unit, and HFP unit is 100 mol%.

  The ratio of each unit in the fluoropolymer A can be determined by NMR analysis such as fusion nuclear magnetic resonance (NMR) analysis, fluorine content analysis, infrared absorption spectrum analysis, or the like. For example, as described in JP-A-2007-314720, using a method such as infrared absorption spectrum analysis, the ratio of the adhesive functional group-containing units in all units constituting the fluoropolymer A (mol%) ).

  The fluoropolymer A can be produced by a conventional method. Examples of the method for producing the fluoropolymer A include the methods described in paragraphs [0053] to [0060] of International Publication No. 2016/017801.

(Silane coupling agent)
At least one surface of the fluororesin layer is preferably treated with a silane coupling agent.
The fact that the surface of the fluororesin layer is treated with a silane coupling agent is that the surface of the fluororesin layer is analyzed by X-ray photoelectron spectroscopy (XPS), and 0.05 atom% or more of silicon atoms are detected. This can be confirmed by detecting 0.05 atom% or more of one or more atoms (nitrogen atom, sulfur atom, etc.) peculiar to the functional group of the coupling agent.

A silane coupling agent is a compound having a hydrolyzable silyl group capable of reacting with an inorganic material and a functional group capable of reacting with an organic material (hereinafter also referred to as “reactive functional group”).
The silanol group (Si-OH) formed by hydrolysis of the hydrolyzable silyl group reacts with the surface of the metal layer, whereby one end of the silane coupling agent is fixed to the surface of the metal layer, and the reactive functional group is By reacting with the surface of the fluororesin layer, the other end of the silane coupling agent is fixed to the fluororesin layer. This improves the adhesion between the metal layer and the fluororesin layer.
In addition, since the unreacted reactive functional group remains on the surface of the fluororesin layer, the affinity between the fluororesin layer and the living tissue is further increased.

  Examples of the hydrolyzable silyl group include a group in which an alkoxy group is bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, and a pentyloxy group.

Examples of the reactive functional group include hydroxyl group, carboxy group, carbonyl group, amino group, amide group, sulfide group, sulfonyl group, sulfo group, sulfonyldioxy group, epoxy group, methacryl group, mercapto group and the like.
As the reactive functional group, those having a nitrogen atom or a sulfur atom are preferable from the viewpoint of further excellent adhesion between the fluororesin layer and the metal layer.

Examples of the reactive functional group having a nitrogen atom include an amino group and a ureido group.
As the silane coupling agent having a reactive functional group having a nitrogen atom, aminoalkoxysilane, ureidoalkoxysilane or a derivative thereof is preferable from the viewpoint of further excellent adhesion between the fluororesin layer and the metal layer.

  As aminoalkoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3- Examples include aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like.

  Examples of aminoalkoxysilane derivatives include ketimine (3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and the like), aminoalkoxysilane salts (N-vinylbenzyl-2-aminoethyl-3- Aminopropyltrimethoxysilane acetate, etc.).

  Examples of the ureidoalkoxysilane include 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, N- (2-ureidoethyl) -3-aminopropyltrimethoxysilane, and the like.

  As the silane coupling agent having a reactive functional group having a nitrogen atom, aminoalkoxysilane having a modified group introduced is preferable from the viewpoint of further excellent adhesion between the fluororesin layer and the metal layer. As the modifying group, a phenyl group is preferable. Examples of the aminoalkoxysilane having a modified group introduced include N-phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane.

Examples of the reactive functional group having a sulfur atom include a mercapto group and a sulfide group.
As the silane coupling agent having a reactive functional group having a sulfur atom, mercaptoalkoxysilane, sulfide alkoxysilane or a derivative thereof is preferable from the viewpoint of further excellent adhesion between the fluororesin layer and the metal layer, and mercaptoalkoxysilane. Or its derivative | guide_body is more preferable.

  Examples of mercaptoalkoxysilanes include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl (dimethoxy) methylsilane, and the like.

  Examples of the sulfide alkoxysilane include bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide.

(Metal layer)
Examples of the metal constituting the metal layer include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy, and the like.
As a metal layer, the layer which consists of metal foil, a metal vapor deposition film, etc. are mentioned.
Examples of the metal foil include rolled copper foil and electrolytic copper foil. On the surface of the metal foil, a rust preventive layer (oxide film such as chromate), a heat-resistant layer or the like may be formed. Moreover, in order to improve adhesiveness with a fluororesin layer, you may process the surface of metal foil with a silane coupling agent.
The thickness of a metal layer should just be the thickness which can exhibit a sufficient function in the use of a base material or a printed wiring board.

(Heat resistant resin layer, fiber reinforced resin layer)
The heat resistant resin layer includes a heat resistant resin.
The heat resistant resin layer may contain components other than the heat resistant resin as necessary within the range not impairing the effects of the present invention.

It is preferable that a heat resistant resin layer consists of a hardened | cured material of a heat resistant resin film or a thermosetting resin, for example.
The heat resistant resin film is a film containing one or more kinds of heat resistant resins, and may be a single layer film or a multilayer film.
Examples of heat-resistant resins include polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, polyallylsulfone (polyethersulfone, etc.), aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, Examples thereof include liquid crystal polyester.

As a heat resistant resin film, a polyimide film and a liquid crystal polyester film are preferable, and a polyimide film is more preferable. You may surface-treat the surface of a heat resistant resin film. Examples of the surface treatment include corona discharge treatment and plasma treatment.
The thickness of the heat resistant resin film is preferably from 0.5 to 100 μm, more preferably from 1 to 50 μm, and even more preferably from 3 to 25 μm, from the viewpoint of the balance between thinning of the printed wiring board and mechanical strength.

As thermosetting resins, epoxy resins, acrylic resins, phenol resins, polyester resins, polyolefin resins, modified polyphenylene ether resins, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimide resins, vinyl Ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, melamine-urea co-condensation resin, fluororesin having a reactive group (excluding fluororesins having an adhesive functional group), thermosetting polyimide And polyamic acid which is a precursor thereof.
As the thermosetting resin, an epoxy resin, an acrylic resin, a bismaleimide resin, a modified polyphenylene ether resin, a thermosetting polyimide, and a polyamic acid that is a precursor thereof are preferable from the viewpoint of being useful for a printed wiring board. A polyphenylene ether resin, a thermosetting polyimide, and a polyamic acid that is a precursor thereof are more preferable. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

The fiber reinforced resin layer includes a matrix resin and reinforcing fibers embedded in the matrix resin. The fiber reinforced resin layer may be a multilayer.
Examples of the matrix resin include a cured product of the thermosetting resin, a heat resistant resin, and the like.
Examples of reinforcing fibers include inorganic fibers and organic fibers. Examples of the inorganic fiber include glass fiber and carbon fiber. Examples of the organic fiber include aramid fiber, polybenzoxazole fiber, polyarylate fiber, and the like.
Examples of the form of the reinforcing fiber include woven fabric and non-woven fabric.

(Manufacturing method of substrate)
When the substrate of the present invention is a single layer substrate, the single layer substrate can be produced by, for example, the following method I or method II.
Method I: A liquid composition in which a resin powder containing a fluororesin is dispersed in a liquid medium is applied to the surface of the coating object, dried, and baked to a temperature higher than the melting point of the fluororesin to form a fluororesin layer on the surface of the coating object. After forming the film, the coating object is removed to obtain a fluororesin film.
Method II: A method of obtaining a fluororesin film by molding a resin composition containing a fluororesin by a known melt molding method (extrusion molding method or the like).

When the substrate of the present invention is a laminated substrate, the laminated substrate can be produced, for example, by the following method III or method IV.
Method III: A liquid composition in which a resin powder containing a fluororesin is dispersed in a liquid medium is applied to the surface of the coating object, dried, and baked to a temperature equal to or higher than the melting point of the fluororesin to form a fluororesin layer on the surface of the coating object. How to form.
Method IV: A method in which a fluororesin film is laminated on the surface of the object to be laminated while being heated to the melting point of the fluororesin or higher to provide a fluororesin layer on the surface of the object to be coated.

In the methods I to IV, the obtained substrate may be annealed.
In the methods I to IV, the surface of the fluororesin layer of the obtained substrate may be treated with a silane coupling agent.
In the methods I to IV, the surface of the fluororesin layer of the obtained substrate may be subjected to plasma treatment.
In the methods III to IV, an object to be laminated may be further laminated on the surface of the fluororesin layer of the obtained base material.

  Examples of the object to be coated and the object to be laminated include a metal foil, a heat resistant resin film, and a prepreg that is a precursor of a fiber reinforced resin. You may surface-treat the surface of a coating target object and a lamination target object beforehand. Examples of the surface treatment include corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling agent treatment, and surface roughening treatment.

  As the coating method in Method I and Method III, spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Examples include the Mayer bar method and the slot die coating method.

In the drying in the method I and the method III, it is not always necessary to completely volatilize the liquid medium, and it may be volatilized to such an extent that the coating film can stably maintain the film shape. In drying, it is preferable to volatilize 50% by mass or more of the liquid medium contained in the liquid composition.
Drying may be performed in one stage, or may be performed in two or more stages at different temperatures.
Examples of the drying method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.

The drying temperature is preferably 50 to 150 ° C, more preferably 80 to 100 ° C. If the drying temperature is at least the lower limit of the above range, the productivity is good. If a drying temperature is below the upper limit of the said range, a liquid medium will volatilize and a fluororesin will be fixed to the surface of a coating target object. The drying temperature is the temperature of the atmosphere.
The drying time is preferably from 0.1 to 30 minutes, more preferably from 0.5 to 20 minutes.

In the firing in the method I and the method III, by melting the fluororesin, individual particles of the resin powder can be melted and integrated to form a homogeneous fluororesin layer.
Examples of the firing method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays. In order to improve the smoothness of the surface of the fluororesin layer, pressurization may be performed with a heating plate, a heating roll, or the like.
The atmosphere during firing is preferably an inert gas atmosphere and more preferably a reducing atmosphere from the viewpoint of suppressing oxidation of the object to be coated.

The firing temperature is preferably equal to or higher than the melting point of the fluororesin, more preferably 300 ° C. or higher, further preferably 330 to 380 ° C., and particularly preferably 350 to 370 ° C. When the firing temperature is at least the lower limit of the above range, the fluororesin can be sufficiently melted. When the firing temperature is equal to or lower than the upper limit of the above range, it is possible to sufficiently melt while suppressing generation of hydrofluoric acid and suppressing damage to the apparatus. The firing temperature is the temperature of the atmosphere.
The firing time is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 1 to 1 minute 30 seconds. When the firing time is at least the lower limit of the above range, the fluororesin can be sufficiently melted. If the firing time is less than or equal to the upper limit of the above range, productivity is good.

Examples of the lamination method in Method IV include a method of hot pressing a lamination object and a fluororesin film.
The pressing temperature is preferably equal to or higher than the melting point of the fluororesin, more preferably 310 to 400 ° C, further preferably 320 to 380 ° C, particularly preferably 330 to 370 ° C. If the press temperature is within the above range, the laminate object and the fluororesin film can be sufficiently bonded while suppressing the thermal deterioration of the fluororesin film.

The press pressure is preferably 0.2 MPa or more, more preferably 0.5 MPa or more, and further preferably 1 MPa or more. The press pressure is preferably 10 MPa or less. When the pressing pressure is within the above range, sufficient adhesion can be obtained between the lamination object and the fluororesin film without damaging the lamination object or the fluororesin film.
The hot pressing is preferably performed in a vacuum atmosphere. The degree of vacuum is preferably 100 kPa or less, more preferably 50 kPa or less, and further preferably 20 kPa or less. If the degree of vacuum is within the above range, bubbles can be prevented from being mixed into the interface between the laminated object and the fluororesin film, and deterioration due to oxidation can also be suppressed.

Examples of the method of treating the surface of the fluororesin layer with a silane coupling agent include a method of applying a treatment liquid containing a silane coupling agent to the surface of the fluororesin layer and drying it.
The treatment liquid contains a silane coupling agent and a solvent (alcohol, toluene, hexane, water, etc.). The concentration of the silane coupling agent in the treatment liquid is preferably from 0.1 to 5% by mass, and more preferably from 0.5 to 3% by mass. 0.5-1.5 mass% is further more preferable.

Examples of the method for applying the treatment liquid include known methods, and a method of immersing a metal foil in the treatment liquid is preferable. The temperature of the treatment liquid during immersion is preferably 20 to 40 ° C., and the immersion time is preferably 10 to 30 seconds.
Drying may be natural drying or forced drying, and natural drying is preferred.
It is preferable to heat-treat after drying. The heat treatment is performed, for example, by heating at 100 to 130 ° C. for 1 to 10 minutes.

  The plasma irradiation apparatus used for the plasma treatment of the surface of the fluororesin layer includes a high frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, an ICP type high An apparatus employing a density plasma type or the like can be mentioned.

Examples of the gas used for the plasma treatment include oxygen gas, nitrogen gas, rare gas (argon gas), hydrogen gas, ammonia gas, and the like, rare gas or nitrogen is preferable, and argon is particularly preferable. One type of gas may be used alone, or two or more types may be mixed and used.
The gas used for the plasma treatment is preferably argon gas, a mixed gas of argon gas and hydrogen gas or nitrogen gas, or a mixed gas of argon gas, nitrogen gas and hydrogen gas. The oxygen gas concentration during the plasma treatment is preferably 500 ppm or less, and may be 0 ppm.

  The atmosphere for the plasma treatment is preferably an atmosphere having a volume fraction of rare gas or nitrogen gas of 50% by volume or more, more preferably 70% by volume or more, still more preferably 90% by volume or more, and 100% by volume. An atmosphere is particularly preferred. If the volume fraction of the rare gas or nitrogen gas is equal to or greater than the lower limit of the above range, it becomes easy to update the surface of the fluororesin layer to a plasma-treated surface with Ra (AFM) of 9.0 nm or more. .

  In plasma processing, Ra (AFM) on the surface of the fluororesin layer increases as processing is performed, but once processing is performed excessively, Ra (AFM) once increased tends to decrease again. For this reason, the processing time is set by controlling the energy (about 1 to 10 eV) of electrons generated by adjusting the gap between the electrodes, the output of the apparatus, and the like so that the processing does not become excessive.

(Liquid composition)
The liquid composition used in Method I and Method III includes a liquid medium and a resin powder dispersed in the liquid medium.
The liquid composition may further contain a resin that is soluble in the liquid medium (hereinafter also referred to as “soluble resin”).
The liquid composition may contain components other than the liquid medium, the resin powder, and the soluble resin (hereinafter, also referred to as “other components”) as necessary, as long as the effects of the present invention are not impaired.

The liquid medium as a dispersion medium is an inert component that is liquid at 25 ° C.
The liquid medium preferably has a lower boiling point than components other than the liquid medium contained in the liquid composition and can be volatilized and removed by heating or the like.

  Examples of the liquid medium include water, alcohol (methanol, ethanol, etc.), nitrogen-containing compounds (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), sulfur-containing compounds (dimethyl sulfoxide, etc.) ), Ether (diethyl ether, dioxane, etc.), ester (ethyl lactate, ethyl acetate, etc.), ketone (methyl ethyl ketone, methyl isopropyl ketone, etc.), glycol ether (ethylene glycol monoisopropyl ether, etc.), cellosolve (methyl cellosolve, ethyl cellosolve, etc.) ) And the like. A liquid medium may be used individually by 1 type, and may use 2 or more types together. The liquid medium is preferably one that does not react with the resin powder.

  The D50 of the resin powder is preferably 0.3 to 6.0 μm, more preferably 0.4 to 5.0 μm, further preferably 0.5 to 4.5 μm, still more preferably 0.7 to 4.0 μm, 1.0-3.5 micrometers is especially preferable. If the D50 of the resin powder is not less than the lower limit of the above range, the resin powder has sufficient fluidity and is easy to handle. If D50 of resin powder is below the upper limit of the said range, it is excellent in the dispersibility to the liquid medium of resin powder. Moreover, the filling rate of the resin powder into the fluororesin layer can be increased, and the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further decreased. Moreover, the thickness of the fluororesin layer can be reduced.

  D90 of the resin powder is preferably 8.0 μm or less, more preferably 6.0 μm or less, and further preferably 1.5 to 5.0 μm. If D90 is less than or equal to the upper limit of the above range, the dispersibility of the resin powder in the liquid medium is excellent. The D90 of the resin powder is preferably close to D50 from the viewpoint of excellent uniformity of the fluororesin layer.

The bulk density of the resin powder is preferably 0.05 g / mL or more, more preferably 0.05 to 0.5 g / mL, and particularly preferably 0.08 to 0.5 g / mL.
The dense bulk density of the resin powder is preferably 0.05 g / mL or more, more preferably 0.05 to 0.8 g / mL, and particularly preferably 0.1 to 0.8 g / mL.
If the loosely packed bulk density or the densely packed bulk density is equal to or higher than the lower limit of the above range, the handling property of the resin powder is further improved. Moreover, the filling rate of the resin powder in the fluororesin layer can be increased. If the loosely packed bulk density or the densely packed bulk density is not more than the upper limit of the above range, it can be used in a general-purpose process.

The resin powder includes a resin powder X containing a fluororesin.
The resin powder may contain a resin powder Y that does not contain a fluororesin, if necessary, as long as the effects of the present invention are not impaired.

  The resin powder preferably contains resin powder X as a main component. If the resin powder X is the main component, the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further reduced. The resin powder containing the resin powder X as a main component means that the ratio of the resin powder X in the resin powder is 80% by mass or more. The ratio of the resin powder X is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass in the resin powder.

  The resin powder X preferably contains a fluororesin as a main component. If a fluororesin is a main component, the relative dielectric constant and dielectric loss tangent of the resin layer can be further reduced. Moreover, the resin powder X with a high bulk density is easy to be obtained. The higher the bulk density of the resin powder X, the better the handling properties. The resin powder X containing a fluororesin as a main component means that the ratio of the fluororesin in the resin powder X is 80% by mass or more. The proportion of the fluororesin is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass in the resin powder X.

  The resin powder X may further contain a component other than the fluororesin as necessary, as long as the effects of the present invention are not impaired. Examples of components other than fluororesins include resins other than fluororesins, inorganic fillers, and rubbers. Examples of the resin other than the fluororesin include aromatic polyester, polyamideimide, thermoplastic polyimide, polyphenylene ether, polyphenylene oxide, and the like.

Resin powder X can be manufactured by the following method, for example.
・ Obtain fluororesin by solution polymerization, suspension polymerization or emulsion polymerization, remove organic solvent or aqueous medium to recover granular fluororesin, and pulverize granular fluororesin as necessary The method of classifying the pulverized product according to the method.
A method of melt-kneading the fluororesin and other components as necessary, pulverizing the kneaded material, and classifying the pulverized material as necessary.

  The resin powder Y not containing a fluororesin preferably contains a resin that does not dissolve in a liquid medium (hereinafter also referred to as “insoluble resin”) as a main component. The resin powder Y mainly composed of an insoluble resin means that the ratio of the insoluble resin in the resin powder Y is 80% by mass or more. The proportion of the insoluble resin is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass in the resin powder Y.

The non-soluble resin that the resin powder Y may contain may be a non-curable resin or a curable resin.
Examples of the non-curable resin include a heat-meltable resin and a non-meltable resin. Examples of the heat-meltable resin include thermoplastic polyimide. Examples of the non-meltable resin include a cured product of a curable resin.
Examples of the curable resin include a polymer having a reactive group, an oligomer having a reactive group, a low molecular compound, and a low molecular compound having a reactive group. Examples of the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group, and an epoxy group.

The soluble resin that may be included in the liquid composition may be a non-curable resin or a thermosetting resin.
Examples of the non-curable resin include a heat-meltable resin and a non-meltable resin. Examples of the heat-meltable resin include thermoplastic polyimide.

As thermosetting resins, epoxy resins, acrylic resins, phenol resins, polyester resins, polyolefin resins, modified polyphenylene ether resins, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimide resins, vinyl Ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, melamine-urea co-condensation resin, fluororesin having a reactive group (excluding fluororesins having an adhesive functional group), thermosetting polyimide And polyamic acid which is a precursor thereof.
As the thermosetting resin, an epoxy resin, an acrylic resin, a bismaleimide resin, a modified polyphenylene ether resin, a thermosetting polyimide, and a polyamic acid that is a precursor thereof are preferable from the viewpoint of being useful for a printed wiring board. A polyphenylene ether resin, a thermosetting polyimide, and a polyamic acid that is a precursor thereof are more preferable. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

  Other components that may be included in the liquid composition include surfactants, antifoaming agents, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, and antistatic agents. Agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, flame retardants, and the like.

  The ratio of the resin powder is preferably 5 to 60% by mass, more preferably 30 to 50% by mass, and still more preferably 35 to 45% by mass in the liquid composition. If the ratio of the resin powder is equal to or higher than the lower limit of the above range, the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further reduced. When the ratio of the resin powder is not more than the upper limit of the above range, the resin powder is easily dispersed uniformly in the liquid composition, and the fluororesin layer is excellent in mechanical strength.

  The ratio of the liquid medium is preferably 15 to 95% by mass, more preferably 15 to 70% by mass, still more preferably 15 to 65% by mass, particularly preferably 20 to 55% by mass in the liquid composition. Mass% is most preferred. If the ratio of a liquid medium exists in the said range, the applicability | paintability of a liquid composition will become favorable. Moreover, if the ratio of a liquid medium is below the upper limit of the said range, since the usage-amount of a liquid medium is small, the external appearance defect of the fluororesin layer resulting from poor drying will not occur easily.

  When a liquid composition contains a soluble resin, 1-50 mass% is preferable among a liquid composition, and, as for the ratio of a soluble resin, 5-30 mass% is more preferable. When the ratio of the soluble resin is not less than the lower limit of the above range, the fluororesin layer is excellent in mechanical strength. If the ratio of the soluble resin is not more than the upper limit of the above range, the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further reduced.

  When the liquid composition contains a surfactant, the ratio of the surfactant is preferably from 0.1 to 30% by mass, more preferably from 3 to 20% by mass, and even more preferably from 5 to 10% by mass in the liquid composition. preferable. When the ratio of the surfactant is not less than the lower limit of the above range, the resin powder is easily dispersed uniformly in the liquid composition. If the ratio of the surfactant is not more than the upper limit of the above range, the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further reduced.

(Mechanism of action)
In the base material of the present invention described above, since it has a fluororesin layer containing a fluororesin that has high affinity with living tissue and is difficult to absorb water, it has high affinity with living tissue and is difficult to absorb water.
In the base material of the present invention, since the fluororesin layer contains a fluororesin having a low relative dielectric constant and dielectric loss tangent, the electrical characteristics are excellent even if the fluororesin layer is thin. Therefore, the base material having the fluororesin layer can be downsized (thinned).
Moreover, in the base material of this invention, since the elongation at the time of the cutting | disconnection at 200 degreeC of a fluororesin layer is 60% or more, a softness | flexibility is high and it is excellent in the followable | trackability with respect to a body movement.
Moreover, in the base material of the present invention, since the elongation at break of the fluororesin layer at 200 ° C. is 400% or less, the fluororesin layer does not extend too much when the body is moved, and in the printed wiring board The displacement between the conductor circuit and the fluororesin layer is suppressed, and the durability against body movement is excellent.

<Printed wiring board>
When the base material of this invention has a metal layer, it can be used for manufacture of a printed wiring board as a copper clad laminated board. The substrate of the present invention may be used by laminating a plurality of sheets.
The printed wiring board of the present invention is obtained by processing the metal layer in the substrate of the present invention into a conductor circuit.

Examples of a method for processing the metal layer into a conductor circuit include the following methods.
A method for processing a metal layer in the substrate of the present invention into a conductor circuit having a predetermined pattern by etching or the like.
A method for forming a conductor circuit by electrolytic plating by a semi-additive method (SAP method) or a modified semi-additive method (MSAP method) using the metal layer in the substrate of the present invention.

In the printed wiring board, an interlayer insulating film may be formed on the conductor circuit, and a conductor circuit may be further formed on the interlayer insulating film. The interlayer insulating film can be formed of, for example, a liquid composition.
In the printed wiring board, a solder resist may be laminated on the conductor circuit. The solder resist can be formed by a liquid composition, for example.
In the printed wiring board, a coverlay film may be laminated on the conductor circuit.
Electronic components (IC chip, resistor, inductor, capacitor, etc.) and the like may be provided on the printed wiring board.
The surface of the printed wiring board may be covered with the base material of the present invention.

FIG. 4 is a cross-sectional view showing an example of the printed wiring board of the present invention.
The printed wiring board 31 includes an adhesive layer 42 on the surface of the fluororesin layer 20, the conductor circuit 22 a formed on the surface of the fluororesin layer 20, and the fluororesin layer 20 and the conductor circuit 22 a other than the region where the electronic component 40 is provided. The coverlay film 44 attached via the electronic component 40, the electronic component 40 connected to the conductor circuit 22a exposed in the region where the electronic component 40 is provided via the terminal 46, and the electronic component 40 in the region where the electronic component 40 is provided. An underfill resin 48 filled between the fluororesin layer 20 and the conductor circuit 22a is included.

FIG. 5 is a cross-sectional view showing another example of the printed wiring board of the present invention.
The printed wiring board 32 is formed on the surface of the heat-resistant resin layer or fiber reinforced resin layer 24, the fluororesin layer 20 provided on the surface of the heat-resistant resin layer or fiber-reinforced resin layer 24, and the surface of the fluororesin layer 20. The conductive circuit 22a, the fluororesin layer 20 other than the region where the electronic component 40 is provided, the coverlay film 44 adhered to the surface of the conductive circuit 22a via the adhesive layer 42, and the region where the electronic component 40 is provided. The electronic component 40 connected to the conductor circuit 22a via the terminal 46, and the underfill resin 48 filled between the electronic component 40 and the fluororesin layer 20 and the conductor circuit 22a in the region where the electronic component 40 is provided. .

(Mechanism of action)
Since the printed wiring board of the present invention described above has a fluororesin layer containing a fluororesin that has a high affinity with living tissue and is difficult to absorb water, it has a high affinity with living tissue and is difficult to absorb water.
In the printed wiring board of the present invention, since the fluororesin layer contains a fluororesin having a low relative dielectric constant and dielectric loss tangent, the electrical characteristics are excellent even if the fluororesin layer is thin. Therefore, the printed wiring board having the fluororesin layer can be downsized (thinned).
Moreover, in the printed wiring board of this invention, since the elongation at the time of cutting | disconnection at 200 degreeC of a fluororesin layer is 60% or more, a softness | flexibility is high and it is excellent in the followable | trackability with respect to a body movement.
Moreover, in the printed wiring board of the present invention, the elongation at the time of cutting of the fluororesin layer at 200 ° C. is 400% or less, so that the fluororesin layer does not extend too much when the body is moved. The displacement between the conductor circuit and the fluororesin layer is suppressed, and the durability against body movement is excellent.

(Use)
The base material and printed wiring board of the present invention are used for a biological contact device, a biological implant device, or an artificial organ.
Examples of the biological contact device include a biological information measurement device (Patent Document 1), a wearable device (International Publication No. 2017/203865), a wearable antenna (Japanese Patent No. 5294667), and the like.
Examples of the biological implantable device include a biological information measuring device (Patent Document 1), an in-vivo sensor assembly (Japanese Patent No. 5802665), an in-vivo implantable electronic device (Japanese Patent Laid-Open No. 3-254760), and an IC chip (Patent). No. 4459980).
Examples of the artificial organ include an artificial blood vessel, an artificial heart, an artificial lung, an artificial liver, an artificial kidney, an artificial pancreas, and an artificial skin (Patent Document 1, Patent Document 2, etc.).

Examples of use of the substrate and the printed wiring board of the present invention in a biological contact device include a printed wiring board in a biological contact device control device and sensor, a casing of the biological contact device, and a member for mounting the biological contact device on the body Etc.
Examples of use of the substrate and the printed wiring board of the present invention in a biological implantable device include a printed wiring board in a control device or sensor of the biological implantable device, a housing of the biological implantable device, and a biological implantable device fixed in the body. For example, a member or the like may be used.
Examples of use of the substrate and printed wiring board of the present invention in an artificial organ include materials for members (body, tube, pump, etc.) constituting the artificial organ, printed wiring boards and artificial organs in artificial organ control devices and sensors. Examples include members for fixing in the body.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1 to 3 are examples.

(Ratio of each unit in the fluoropolymer)
The proportion of NAH units was determined by infrared absorption spectrum analysis. The proportion of units other than NAH units was determined by melt NMR analysis and fluorine content analysis.

(Infrared absorption spectrum analysis)
The fluoropolymer was press molded to obtain a film having a thickness of 200 μm. The film was analyzed by infrared spectroscopy to obtain an infrared absorption spectrum. In the infrared absorption spectrum, an absorption peak of NAH units in the fluoropolymer appears at 1778 cm ⁻¹ . The absorbance of this absorption peak was measured, and the ratio of NAH units in the fluoropolymer was determined using the NAH molar extinction coefficient of 20810 mol ⁻¹ · L · cm ⁻¹ .

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

(MFR)
Using a melt indexer (manufactured by Techno Seven), the mass (g) of the fluoropolymer flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 49 N in 10 minutes was determined as MFR. .

(Specific dielectric constant and dielectric loss tangent)
In accordance with the transformer bridge method in accordance with ASTM D 150, dielectric breakdown test equipment (Yamayo test) in a test environment in which the temperature is maintained within a range of 23 ° C. ± 2 ° C. and the relative humidity within a range of 50% ± 5% RH. A value obtained at 1 MHz using YSY-243-100RHO manufactured by Kikai Co., Ltd. was defined as a relative dielectric constant (1 MHz). Further, in a higher frequency band, a specific permittivity (20 GHz) at a frequency of 20 GHz and an environment within a range of 23 ° C. ± 2 ° C. and 50 ± 5% RH by SPDR (split post dielectric resonator) method and The dielectric loss tangent was measured.

(Fluoropolymer D50)
In order from the top, 2.000 mesh sieve (mesh 2.400 mm), 1.410 mesh sieve (mesh 1.705 mm), 1.000 mesh sieve (mesh 1.205 mm), 0.710 mesh sieve (mesh) 0.855 mm), 0.500 mesh sieve (0.605 mm mesh), 0.250 mesh sieve (0.375 mm mesh), 0.149 mesh sieve (0.100 mm mesh), and a tray. The fluoropolymer was put on the top sieve and sieved with a shaker for 30 minutes. The mass of the fluorinated polymer remaining on each sieve is measured, and the cumulative amount of passing mass with respect to each opening value is shown in a graph. The particle diameter at which the cumulative amount of passing mass is 50% is obtained, and this is calculated as the fluorinated weight. Combined D50.

(D50 and D90 of resin powder)
Using a laser diffraction / scattering particle size distribution measuring device (Horiba, Ltd., LA-920 measuring instrument), resin powder was dispersed in water, the particle size distribution was measured, and D50 and D90 were calculated.

(Sparsely packed bulk density and densely packed bulk density)
The loosely packed bulk density and the densely packed bulk density of the resin powder were measured by the method described in paragraphs [0117] and [0118] of International Publication No. 2016/017801.

(Arithmetic mean roughness Ra)
Based on JIS B 0601: 2013 (corresponding international standard ISO 4287: 1997, Amd. 1: 2009), the arithmetic average roughness Ra of the surface of the fluororesin layer of the single-sided copper-clad laminate was measured. The reference length lr (cut-off value λc) for the roughness curve when calculating the arithmetic average roughness Ra was 0.8 mm.

(Ra (AFM) and Rz (AFM))
Using an AFM manufactured by Oxford Instruments, Ra (AFM) and Rz (AFM) of the surface in the 1 μm ² range of the fluororesin layer of the single-sided copper-clad laminate were measured under the following measurement conditions.
Probe: AC160TS-C3 (tip R <7 nm, spring constant 26 N / m),
Measurement mode: AC-Air,
Scan Rate: 1 Hz.

(Wet tension)
The wetting tension of the surface of the fluororesin layer was measured in accordance with JIS K 6768: 1999 using a wetting tension test liquid mixture (manufactured by Wako Pure Chemical Industries, Ltd.).

(Water absorption expansion coefficient, water absorption rate)
A sample of a single-sided copper clad laminate (length 5.0 cm × width 5.0 cm) was left under conditions of 23 ° C. and 50% RH, and the dimensional change and mass change of the sample were measured over time. The hygroscopic expansion coefficient [cm / cm / (% RH)] was calculated from the dimensional change of the sample. The water absorption rate (%) was calculated from the water absorption amount when the mass change of the sample ceased.

(Elongation at cutting)
A test piece was obtained by punching a base material consisting only of a fluororesin layer into an ASTM No. 5 dumbbell shape. The test piece was cut at a temperature of 200 ° C. and a tensile speed of 500 mm / min according to JIS K 6251: 2010 (corresponding international standard ISO 37: 2005) using a tensile tester (Orientec Co., Ltd., Tensilon). Elongation was measured.

(Peel test)
A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the laminate 1. The fluororesin layer and the fiber reinforced resin layer were peeled from one end in the length direction of the test piece to a position of 50 mm. Using a tensile tester (Orientec Co., Ltd.) with a position of 50 mm from one end in the length direction of the test piece as the center, peeling is performed 90 degrees at a pulling speed of 50 mm / min, and the maximum load is peel strength (N / cm ).

(Flexibility)
Based on the folding strength test method (according to JIS P 8115: 2001) for the laminate 2, the bending radius: 0.38 mm, the load: 500 g (4.9 N), the bending speed: 175 times / Min, bending angle: bending was repeated for 15 minutes under the condition of 135 °. About the laminated body 2 which performed bending repeatedly, the presence or absence of peeling between a polyimide film and a single-sided copper clad laminated board was confirmed.

(Production of fluoropolymer A)
Using TFE, NAH (manufactured by Hitachi Chemical Co., Ltd., hymic anhydride), PPVE (manufactured by Asahi Glass Co., Ltd.), a fluoropolymer A-1 is produced by the procedure described in paragraph [0123] of International Publication No. 2016/017801. did. The ratio of each unit in the fluoropolymer A-1 was NAH unit / TFE unit / PPVE unit = 0.1 / 97.9 / 2.0 (mol%). The melting point of the fluoropolymer A-1 was 300 ° C., the MFR was 17.6 g / 10 min, the relative dielectric constant (1 MHz) was 2.1, and the D50 was 1554 μm.

(Manufacture of resin powder)
Resin powder is obtained by pulverizing the fluoropolymer A-1 using a jet mill (manufactured by Seishin Enterprise Co., Ltd., single track jet mill FS-4 type) under the conditions of pulverization pressure: 0.5 MPa, treatment speed: 1 kg / hour. X-1 was obtained. D50 of the resin powder X-1 was 2.58 μm, and D90 was 7.1 μm. The loosely packed bulk density of the resin powder X-1 was 0.278 g / mL, and the densely packed bulk density was 0.328 g / mL.

(Preparation of liquid composition)
Using a laboratory stirrer (manufactured by Yamato Scientific Co., Ltd., LT-500), 120 g of resin powder X-1, 9 g of nonionic surfactant (manufactured by Neos Co., Ltd., Aftergent 710FM) and 234 g of N, N-dimethylacetamide The liquid composition was obtained by stirring for 60 minutes.

(Example 1)
The liquid composition was applied to the surface of the copper foil, dried at 100 ° C. for 15 minutes in a nitrogen atmosphere, heated at 350 ° C. for 15 minutes, and gradually cooled. A single-sided copper clad laminate having a fluororesin layer having a thickness of 5 μm on the surface of the copper foil was obtained. Table 1 shows the water absorption expansion coefficient and water absorption rate of the single-sided copper-clad laminate.
The single-sided copper-clad laminate was immersed in hydrochloric acid, and the copper foil was dissolved with hydrochloric acid to obtain a base material consisting only of a fluororesin layer. Table 1 shows the elongation at break of the base material composed of only the fluororesin layer.

The surface of the fluororesin layer of the single-sided copper-clad laminate was plasma treated. As the plasma processing apparatus, AP-1000 of NORDSON MARCH was used. The plasma processing conditions were: AP-1000 RF output 300 W, gap between electrodes 2 inches, introduced gas type Argon gas (Ar), introduced gas flow rate 50 cm ³ / min, pressure 13 Pa, treatment time 1 Minutes. The arithmetic average roughness Ra of the surface of the fluororesin layer after the plasma treatment was 2.5 μm, Ra (AFM) was 14.5 nm, Rz (AFM) was 195 nm, and the wetting tension was 54 mN / m. The wetting tension of the surface of the fluororesin layer not subjected to plasma treatment was 22.6 mN / m or less.

FR-4 (manufactured by Hitachi Chemical Co., Ltd., reinforced fiber: glass fiber, matrix resin: epoxy resin, product name: GEA- on the fluororesin layer side of the single-sided copper-clad laminate within 72 hours after the plasma treatment is performed. 67N 0.2t (HAN), thickness: 0.2mm), metal layer / fluororesin layer / fiber reinforced by vacuum hot pressing under conditions of press temperature 185 ° C, press pressure 3.0MPa, press time 60min The laminated body 1 which consists of a resin layer was obtained. The relative dielectric constant (20 GHz) was 4.32, and the dielectric loss tangent (measurement frequency: 20 GHz) was 0.01568. In addition, when it did not have a fluororesin layer (when copper foil and GEA-67N are in direct contact), the dielectric constant (20 GHz) was 4.56, and the dielectric loss tangent (measurement frequency: 20 GHz) was 0.01574. . By the way, this time, the plasma treatment was performed and the prepreg was laminated within 72 hours, but the effect of the plasma treatment continues for one year.
Table 1 shows the peel strength between the fluororesin layer and the fiber reinforced resin layer in the laminate 1.

A single-sided copper-clad laminate and a 12.5 μm thick polyimide film (Ube Industries, Upilex) are laminated so that the polyimide film and the fluororesin layer are in contact with each other, and the temperature is 360 ° C. and the pressure is 10 MPa for 5 minutes. The laminate 2 was obtained by pressing.
The evaluation results of the flexibility of the laminate 2 are shown in Table 1.

(Example 2)
A single-sided copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the fluororesin layer was changed to 7 μm. Table 1 shows the water absorption expansion coefficient and water absorption rate of the single-sided copper-clad laminate.
Except having used the single-sided copper clad laminated board of Example 2, the base material which consists only of a fluororesin layer was obtained like Example 1. FIG. Table 1 shows the elongation at break of the base material composed of only the fluororesin layer.
A laminate 1 was obtained in the same manner as in Example 1 except that the single-sided copper-clad laminate of Example 2 was used. Table 1 shows the peel strength between the fluororesin layer and the fiber reinforced resin layer in the laminate 1.
A laminate 2 was obtained in the same manner as in Example 1 except that the single-sided copper-clad laminate of Example 2 was used. The evaluation results of the flexibility of the laminate 2 are shown in Table 1.

(Example 3)
A single-sided copper clad laminate was obtained in the same manner as in Example 1 except that the thickness of the fluororesin layer was changed to 14 μm. Table 1 shows the water absorption expansion coefficient and water absorption rate of the single-sided copper-clad laminate.
A base material composed only of a fluororesin layer was obtained in the same manner as in Example 1 except that the single-sided copper-clad laminate of Example 3 was used. Table 1 shows the elongation at break of the base material composed of only the fluororesin layer.
A laminate 1 was obtained in the same manner as in Example 1 except that the single-sided copper-clad laminate of Example 3 was used. Table 1 shows the peel strength between the fluororesin layer and the fiber reinforced resin layer in the laminate 1.
A laminate 2 was obtained in the same manner as in Example 1 except that the single-sided copper-clad laminate of Example 3 was used. The evaluation results of the flexibility of the laminate 2 are shown in Table 1.

  The base material and printed wiring board of the present invention are used for a biological contact device, a biological implant device, or an artificial organ.

  DESCRIPTION OF SYMBOLS 11 Base material, 12 Base material, 13 Base material, 20 Fluororesin layer, 22 Metal layer, 22a Conductor circuit, 24 Heat resistant resin layer or fiber reinforced resin layer, 31 Printed wiring board, 32 Printed wiring board, 40 Electronic component, 42 adhesive layer, 44 coverlay film, 46 terminals, 48 underfill resin.

Claims (11)

It is a substrate used for a biological contact device, a biological implant device or an artificial organ,
The substrate has a fluororesin layer containing a fluororesin,
The base material whose elongation at the time of the cutting | disconnection in 200 degreeC of the said fluororesin layer is 20 to 400%.   The fluororesin is a fluororesin having a melting point of 260 ° C. or higher and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group. The base material according to claim 1.   The base material according to claim 1 or 2, wherein at least one surface of the fluororesin layer is treated with a silane coupling agent.   The substrate according to any one of claims 1 to 3, further comprising a metal layer in contact with the fluororesin layer.   The base material of Claim 4 whose peeling strength of the said fluororesin layer and the said metal layer is 5 N / cm or more.   The base material according to claim 4 or 5, further comprising one or both of a heat resistant resin layer and a fiber reinforced resin layer in contact with the fluororesin layer.   The base material of Claim 6 whose peeling strength of the said fluororesin layer and the said heat resistant resin layer or the said fiber reinforced resin layer is 5 N / cm or more.   The printed wiring board formed by processing the said metal layer in the base material as described in any one of Claims 4-7 into a conductor circuit.   A biological contact device comprising the substrate according to any one of claims 1 to 7 or the printed wiring board according to claim 8.   A biological implantable device comprising the substrate according to any one of claims 1 to 7 or the printed wiring board according to claim 8.   An artificial organ comprising the substrate according to any one of claims 1 to 7 or the printed wiring board according to claim 8.

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