JP2019181735A - Manufacturing method of laminate and manufacturing method of substrate - Google Patents

Abstract

To provide a method capable of manufacturing a laminate excellent in dimensional stability and electric characteristic, and excellent in adhesiveness with an inorganic layer and a fluorine resin layer, and a manufacturing method of a substrate suitably used in manufacturing the laminate.SOLUTION: There is provided a method for manufacturing a laminate 11 having an inorganic layer 20 having resistivity at 25°C of 10Ω cm or more, and a fluorine resin layer 22 arranged on a surface of the inorganic layer 20 and containing following fluorine resin, including: a surface treatment of one or both of a surface of the inorganic layer 20 of a first substrate having the inorganic layer 20, and a surface of the fluorine resin layer 22 of a second substrate having the fluorine resin layer 22, and thermal compression bond of the first substrate and the second substrate with the inorganic layer 20 and the fluorine resin layer 22 in contact at melting point of the fluorine resin or higher. Fluorine resin: a fluorine resin having at least one kind functional group selected from a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group, and capable of being melting molded.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate manufacturing method and a substrate manufacturing method used in the laminate manufacturing method.

  There is an increasing demand for thinner and lighter electronic devices, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components on a semiconductor package or printed wiring board corresponding to the reduction in thickness and density, it is important to suppress warpage that occurs during mounting. In order to suppress the warpage of the semiconductor package or printed wiring board when mounting electronic components, the thermal expansion coefficient of the laminate used for the semiconductor package or printed wiring board should be brought close to the thermal expansion coefficient of the electronic component and the elastic modulus of the laminate. In other words, it is desired to improve the dimensional stability of the laminate.

As a laminate for a printed wiring board having excellent dimensional stability, a laminate in which a glass film and a copper-clad laminate made of an epoxy resin and a copper foil are laminated has been proposed (Patent Document 1).
Moreover, as a laminate for a printed wiring board having excellent dimensional stability and electrical characteristics, a copper-clad laminate comprising an inorganic substrate (glass substrate, ceramic substrate, semiconductor substrate), a fluororesin film, polyimide and copper foil Have been proposed (Patent Document 2).

Japanese translation of PCT publication No. 2004-512667 JP 2011-11457 A

Since the laminate described in Patent Document 1 does not have a fluororesin layer, the electrical characteristics are insufficient. Therefore, the semiconductor package and printed wiring board using the laminated body described in Patent Document 1 cannot sufficiently cope with the frequency in the high frequency band.
The laminate described in Patent Document 2 has insufficient adhesion between the inorganic substrate and the fluororesin film.

  The present invention provides a method capable of producing a laminate having excellent dimensional stability and electrical characteristics and excellent adhesion between an inorganic layer and a fluororesin layer, and a method for producing a substrate suitably used for producing the laminate. To do.

The present invention has the following aspects.
<1> A method for producing a laminate having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more and a fluororesin layer containing the following fluororesin provided on the surface of the inorganic layer. Any one or both of the surface of the inorganic layer of the first base material having the inorganic layer and the surface of the fluororesin layer of the second base material having the fluororesin layer, The manufacturing method of a laminated body which thermocompression-bonds 1 base material and the said 2nd base material more than melting | fusing point of the said fluororesin in the state which the said inorganic layer and the said fluororesin layer contacted.
Fluororesin: A fluororesin that has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group and is melt-moldable.
<2> The method for producing a laminate according to <1>, wherein one or both of the surface of the inorganic layer and the surface of the fluororesin layer is subjected to plasma treatment.
<3> The method for producing a laminate according to <1>, wherein the surface of the inorganic layer is wet-treated.
<4> The method for producing a laminate according to <1>, wherein the surface of the inorganic layer is wet-treated, and the surface of the fluororesin layer is plasma-treated.
<5> Any one of <1> to <4>, wherein the first base material and the second base material are thermocompression bonded at a pressure equal to or higher than a melting point of the fluororesin and equal to or higher than 0.2 MPa. The manufacturing method of the laminated body.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein the fluororesin is a fluorocopolymer having a unit based on tetrafluoroethylene.
<7> The laminate according to any one of <1> to <6>, wherein the surface of the inorganic layer is surface-treated, and the surface-treated inorganic layer has an arithmetic average roughness Ra of 1.0 μm or less. Manufacturing method.
<8> The method for producing a laminate according to any one of <1> to <7>, wherein the material of the inorganic layer is glass, ceramics, or a semiconductor.
<9> The first base material has only the inorganic layer, or the first base material has the inorganic layer in both outermost layers, and the first base material is the two second layers. The method for producing a laminate according to any one of <1> to <8>, wherein the laminate is thermocompression-bonded between the substrates.
<10> The second base material has only the fluororesin layer, and after the first base material and the second base material are thermocompression-bonded or simultaneously press-bonded, on the surface of the fluororesin layer. The manufacturing method of the laminated body in any one of said <1>-<9> which laminates | stacks metal foil.
<11> The method for producing a laminate according to any one of <1> to <9>, wherein the second base material further includes a metal layer made of a metal foil.
<12> The method for producing a laminate according to any one of <1> to <11>, wherein holes are formed in the inorganic layer.
<13> A first base material having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more, and a second base material having a fluororesin layer, the inorganic layer and the fluororesin layer The first substrate is a method for producing the first substrate used for thermocompression bonding in a state where the substrate is in contact with the surface, and the surface of the inorganic layer of the first substrate is wet-treated or plasma-treated. Manufacturing method.
<14> a first base material having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more, and a second base material having a fluororesin layer containing the following fluororesin: A method for producing the second base material used when thermocompression bonding is performed in a state where the fluororesin layer is in contact with the second base material, wherein the surface of the fluororesin layer of the second base material is subjected to plasma treatment. The manufacturing method of the base material.
Fluororesin: A fluororesin that has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group and is melt-moldable.

According to the method for producing a laminate of the present invention, it is possible to produce a laminate having excellent dimensional stability and electrical characteristics and excellent adhesion between an inorganic layer and a fluororesin layer.
According to the method for producing a substrate of the present invention, a substrate suitably used for the method for producing a laminate of the present invention can be produced.

It is sectional drawing which shows an example of the laminated body in this invention. It is sectional drawing which shows the other example of the laminated body in this invention. It is sectional drawing which shows the other example of the laminated body in this invention. It is sectional drawing which shows the other example of the laminated body in this invention. 6 is a scanning electron micrograph of the cross section of the laminate after the peel test of Example 6. FIG. 2 is a scanning electron micrograph of the cross section of the laminate after the peel test of Example 12. FIG.

The following definitions of terms apply throughout this specification and the claims.
“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.
“MFR” is a melt mass flow rate defined in JIS K 7210-1: 2014 (corresponding international standard ISO 1133-1: 2011).
“Melting point” means the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
"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 a value obtained at 1 MHz using a dielectric breakdown test apparatus. 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.
“Resistivity at 25 ° C.” is an average value obtained by measuring five or more points of a sample using probes having a probe interval of 5 mm arranged in a straight line at equal intervals in accordance with JIS K 7194-1994.
The “arithmetic average roughness Ra” is measured based on JIS B 0601: 2013 (corresponding international standard ISO 4287: 1997, Amd. 1: 2009). The reference length lr (cutoff value λc) for the roughness curve when 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). Ra (AFM) is a value measured using an AFM manufactured by Oxford Instruments.
The “carbonyl group-containing group” means a group having a carbonyl group (—C (═O) —) in the structure.
The “acid anhydride group” means a group represented by —C (═O) —O—C (═O) —.
“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.
“˜” 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 4 are different from actual ones for convenience of explanation.

<Laminated body>
The laminate obtained by the production method of the present invention has an inorganic layer and a fluororesin layer provided on the surface of the inorganic layer.
The laminate preferably further has a metal layer provided on the surface of the fluororesin layer.
The laminated body may have a layer other than the inorganic layer, the fluororesin layer, and the metal layer (hereinafter also referred to as “other layer”) as necessary within a range not impairing the effects of the present invention.

FIG. 1 is a cross-sectional view showing an example of a laminate in the present invention.
The laminate 11 includes an inorganic layer 20 and a fluororesin layer 22 provided on the first surface of the inorganic layer 20.

FIG. 2 is a cross-sectional view showing another example of the laminate in the present invention.
The laminate 12 includes an inorganic layer 20, a fluororesin layer 22 provided on the first surface of the inorganic layer 20, and a metal layer 24 provided on the surface of the fluororesin layer 22.

FIG. 3 is a cross-sectional view showing another example of the laminate in the present invention.
The laminate 13 includes an inorganic layer 20 and a fluororesin layer 22 provided on each of the first surface and the second surface of the inorganic layer 20.

FIG. 4 is a cross-sectional view showing another example of the laminate in the present invention.
The laminate 14 includes an inorganic layer 20, a fluororesin layer 22 provided on each of the first surface and the second surface of the inorganic layer 20, and a metal layer 24 provided on the surface of the fluororesin layer 22. Have.

(Inorganic layer)
An inorganic layer is a layer originating in the inorganic layer in the base material used with the manufacturing method of this invention.
Holes such as through holes and via holes may be formed in the inorganic layer.

The resistivity of the inorganic layer at 25 ° C. is 10 ² Ω · cm or more, preferably 10 ³ Ω · cm or more, and more preferably 10 ⁵ Ω · cm or more. If the resistivity of the inorganic layer at 25 ° C. is not less than the above range, the metal layer is excluded. An inorganic layer made of an inorganic material other than metal can be suitably used as a substrate in a semiconductor package or a printed wiring board. The higher the resistivity at 25 ° C. of the inorganic layer, the better, and the upper limit is not limited.

As the material for the inorganic layer, glass, ceramics, or semiconductor is preferable, and glass is more preferable because it is suitable as a substrate in a semiconductor package or a printed wiring board.
Examples of the glass include soda lime glass, soda potash glass, soda aluminum silicate glass, aluminoborate glass, aluminoborosilicate glass, low expansion glass, quartz glass, and porous glass.

Examples of the ceramic include alumina, zirconia, mullite, cordierite, steatite, magnesium titanate, calcium titanate, strontium titanate, aluminum nitride, silicon carbide, and silicon nitride.
Semiconductors include silicon, germanium, selenium, tin, tellurium, GeAs, GaP, GaSb, AlP, AlAs, AlSb, InP, InAs, InSb, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlGaAs, GaInAs, AlInAs, AlGaInAs etc. are mentioned.

  The thickness of the inorganic layer is preferably 0.05 to 2.00 mm, more preferably 0.10 to 1.00 mm, and further preferably 0.20 to 0.70 mm. If the thickness of the inorganic layer is not less than the lower limit of the above range, the dimensional stability of the laminate is further improved. If the thickness of the inorganic layer is not more than the upper limit of the above range, the semiconductor package and the printed wiring board can be sufficiently thinned.

(Fluorine resin layer)
The fluororesin layer is a fluororesin layer formed by the production method of the present invention.
The fluororesin layer includes a specific fluororesin (hereinafter also referred to as “fluororesin A”).
The fluororesin layer may contain an inorganic filler, a resin other than the fluororesin A, an additive, and the like as required, as long as the effects of the present invention are not impaired.

  The proportion of the fluororesin A in the fluororesin layer is preferably 80% by mass or more, and more preferably 90% by mass or more. The upper limit of the ratio of the fluororesin A is 100% by mass. If the ratio of the fluororesin A is not less than the lower limit of the above range, the electrical properties of the laminate are further improved.

  The thickness of the fluororesin layer is preferably 1 to 1000 μm, more preferably 2 to 500 μm, and still more preferably 5 to 50 μm. If the thickness of the fluororesin layer is not less than the lower limit, the electrical properties of the laminate are further improved. If the thickness of the fluororesin layer is not more than the above upper limit value, the semiconductor package and the printed wiring board can be sufficiently thinned.

  The relative dielectric constant (measurement frequency: 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 of the fluororesin layer is not more than the upper limit of the above range, the laminate can be suitably used for semiconductor packages and printed wiring boards that require a low dielectric constant. If the relative dielectric constant of the fluororesin layer is not less than the lower limit of the above range, both the electrical properties and the adhesiveness of the fluororesin layer are excellent.

Ra (AFM) on the surface of the fluororesin layer is preferably 3.0 nm or more, more preferably 8.0 nm or more, and further preferably 12 nm or more. If Ra (AFM) of the surface of a fluororesin layer is more than the lower limit of the said range, it will be excellent in the adhesiveness of a fluororesin layer and metal foil. Ra (AFM) is preferably 1 μm or less.
Ra (AFM) of the surface of the fluororesin layer is measured on the surface in the range of 1 μm ² using AFM manufactured by Oxford Instruments, 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 fluororesin A can be melt-molded. Since the fluororesin A can be melt-molded, the fluororesin powder is easily melted to form a fluororesin layer in the production method of the present invention described later.
The fluororesin A that can be melt-molded has an MFR of 0.1 to 1000 g / 10 min (preferably 0.5 to 100 g / min) at a temperature of 20 ° C. or higher than the melting point of the fluororesin A under a load of 49 N. Those having a temperature of 10 minutes, more preferably 1 to 30 g / 10 minutes, and still more preferably 5 to 20 g / 10 minutes are preferred. When the MFR is at least the lower limit of the above range, the melt moldability of the fluororesin A is excellent, and the surface smoothness and appearance of the fluororesin layer are excellent. If MFR is below the upper limit of the said range, it will be excellent in the mechanical strength of a fluororesin layer.

  The melting point of the fluororesin A is preferably 150 ° C. or higher, more preferably 200 ° C. or higher and 325 ° C. or lower, further preferably 250 ° C. or higher and 320 ° C. or lower, and particularly preferably 280 ° C. or higher and 315 ° C. or lower. When the melting point of the fluororesin A is not less than the lower limit of the above range, the heat resistance of the laminate is excellent. If the melting point of the fluororesin A is equal to or lower than the upper limit of the above range, a general-purpose apparatus can be used when producing a laminate.

70-80 mass% is preferable and, as for the fluorine content of the fluororesin A, 70-78 mass% is more preferable. The fluorine content is a ratio of the total mass of fluorine atoms to the total mass of the fluororesin A. If fluorine content is more than the said lower limit, it will be excellent in the heat resistance of a fluororesin layer. Moreover, the electrical properties of the laminate are further improved. When the fluorine content is not more than the above upper limit value, the melt moldability of the fluororesin A is excellent. The fluorine content is determined by ¹⁹ F-NMR.

  The relative dielectric constant (measurement frequency: 1 MHz) of the fluororesin A 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 of the fluororesin A, the more excellent the electrical properties of the laminate. The lower limit value of the relative dielectric constant is usually 2.0. The relative dielectric constant of the fluororesin A can be adjusted by the ratio of TFE units.

  The fluororesin A is preferably a fluorine-containing copolymer having units based on tetrafluoroethylene (hereinafter also referred to as “TFE”). If the fluororesin A is a fluorocopolymer having units based on TFE, the electrical properties of the laminate are excellent.

  The fluororesin A has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group (hereinafter also referred to as “adhesive functional group”). Have Since the fluororesin A has an adhesive functional group, the adhesiveness between the fluororesin layer and the inorganic layer or the metal layer is excellent. The adhesive functional group in the fluororesin A may be one type or two or more types.

  Examples of the fluororesin A include a fluorine-containing copolymer having a unit having an adhesive functional group and a terminal group having an adhesive functional group. Examples of the fluorine-containing copolymer having an adhesive functional group include a TFE-perfluoro (alkyl vinyl ether) copolymer (PFA) having an adhesive functional group, and a TFE-hexafluoropropylene copolymer (FEP) having an adhesive functional group. ), An ethylene-TFE copolymer (ETFE) having an adhesive functional group, and polytetrafluoroethylene having an adhesive functional group.

The adhesive functional group in the fluororesin A is preferably a carbonyl group-containing group from the viewpoint of adhesiveness between the fluororesin layer and the inorganic layer or the metal layer.
Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride group.

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. Carbon number of an alkylene group is carbon number which does not contain the carbon atom of a carbonyl group. 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 carbonyl group-containing group, an acid anhydride group and a carboxy group are preferable.

The content of the adhesive functional group in the fluororesin A is preferably 10 to 60000, more preferably 100 to 50000, more preferably 100 to 10000, with respect to 1 × 10 ⁶ main chain carbon atoms of the fluororesin A. 300 to 5000 is particularly preferable. When the content of the adhesive functional group is within the above range, the adhesiveness between the fluororesin layer and the inorganic layer or the metal layer is further improved.
The content of the adhesive functional group can be measured by methods such as nuclear magnetic resonance (NMR) analysis and infrared absorption spectrum analysis. For example, using a method such as infrared absorption spectrum analysis as described in JP-A-2007-314720, the proportion of units having an adhesive functional group in all units constituting the fluorinated copolymer (mol%) ) And the content of the adhesive functional group can be calculated from this ratio.

The adhesive functional group is preferably present as one or both of the end group of the main chain of the fluororesin A and the pendant group of the main chain from the viewpoint of the adhesiveness between the fluororesin layer and the inorganic layer or the metal layer. .
The fluororesin A in which the adhesive functional group is present as one or both of the end group of the main chain and the pendant group of the main chain is used to co-polymerize the monomer having the adhesive functional group during the polymerization of the monomer. It can be produced by a method such as polymerization, a monomer is polymerized using a chain transfer agent or a polymerization initiator that provides an adhesive functional group. These methods can be used in combination. In particular, by copolymerizing a monomer having an adhesive functional group to produce a copolymer having the monomer unit, the fluororesin A in which the adhesive functional group exists at least as a pendant group of the main chain It is preferable that

  As the monomer having an adhesive functional group, a monomer having a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, or an isocyanate group is preferable, and a monomer having an acid anhydride group or a carboxy group is preferable. A monomer is particularly preferred. Specifically, monomers having a carboxy group such as maleic acid, itaconic acid, citraconic acid, undecylenic acid, itaconic anhydride (hereinafter also referred to as “IAH”), citraconic anhydride (hereinafter also referred to as “CAH”). ), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as “NAH”), monomers having an acid anhydride group such as maleic anhydride, hydroxyalkyl vinyl ether, epoxy alkyl vinyl ether, etc. Is mentioned.

As the chain transfer agent that provides an adhesive functional group, a chain transfer agent having a carboxy group, an ester bond, a hydroxyl group, or the like is preferable. Specific examples include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.
As the polymerization initiator that provides an adhesive functional group, peroxide polymerization initiators such as peroxy carbonate, diacyl peroxide, and peroxy ester are preferable. Specific examples include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, tert-butyl peroxyisopropyl carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and the like. .

As the fluororesin A in which the adhesive functional group is present at least as a pendant group of the main chain, the following fluorine-containing copolymer A1 is particularly preferable from the viewpoint of further excellent adhesiveness.
Fluorocopolymer A1: A unit derived from TFE, a unit derived from a cyclic hydrocarbon monomer having an acid anhydride group (hereinafter also referred to as “acid anhydride monomer”), And a fluorine-containing copolymer having units derived from a monomer (excluding TFE).
Hereinafter, the unit derived from TFE is also referred to as “TFE unit”, the unit derived from the acid anhydride monomer as “unit u2”, and the unit derived from the fluorine-containing monomer as “unit u3”.

Examples of the acid anhydride monomer include IAH, CAH, NAH, maleic anhydride and the like. An acid anhydride monomer may be used individually by 1 type, and may use 2 or more types together.
The acid anhydride monomer is preferably at least one selected from the group consisting of IAH, CAH and NAH. When any one of IAH, CAH and NAH is used, a fluorine-containing fluorine-containing acid anhydride group can be used without using a special polymerization method (see Japanese Patent Application Laid-Open No. 11-19313) required when maleic anhydride is used. Copolymer A1 can be easily produced.
As the acid anhydride monomer, IAH and NAH are particularly preferable because the adhesive adhesiveness between the fluororesin layer and the inorganic layer or metal layer is further excellent.

  In the fluorine-containing copolymer A1, a part of the acid anhydride group in the unit u2 is hydrolyzed, and as a result, a dicarboxylic acid (itaconic acid, citraconic acid, 5-norbornene-2 corresponding to the acid anhydride monomer is obtained. , 3-dicarboxylic acid, maleic acid, etc.) units. When a dicarboxylic acid unit is included, the content of the dicarboxylic acid unit is included in the content of the unit u2.

The fluorine-containing monomer constituting the unit u3 is preferably a fluorine-containing compound having one polymerizable carbon-carbon double bond, and is a fluoroolefin (chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene). , Hexafluoropropylene (hereinafter also referred to as “HFP”), hexafluoroisobutylene, etc., excluding TFE), CF ₂ = CFOR ^f1 (where R ^f1 is a C 1-10 perfluoroalkyl group, or A group containing an oxygen atom between carbon atoms of a C 2-10 perfluoroalkyl group (hereinafter also referred to as “PAVE”), CF ₂ = CFOR ^f ₂ SO ₂ X ¹ (where R ^f2 is carbon Between the carbon atoms of a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 2 to 10 carbon atoms A group containing atom, ^{X 1} is a halogen atom or a hydroxyl ^{_{group.), CF 2 = CFOR f3}} CO 2 X 2 ( provided ^{that, R f3} is a perfluoroalkyl group having 1 to 10 carbon atoms, or carbon atoms 2 10 is a group containing an oxygen atom between carbon atoms of the perfluoroalkyl group, and X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.), CF ₂ ═CF (CF ₂ ) _p OCF═CF ₂ (Here, p is 1 or ^{_{2.), CH 2 = CX}} 3 (CF 2) q X 4 ( however, ^{X 3} is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, X ⁴ is a hydrogen atom or a fluorine atom (hereinafter also referred to as “FAE”), a fluorine-containing monomer having a ring structure (perfluoro (2,2-dimethyl-1,3-dioxole), 2,2 , 4-Trifluoro-5- Li fluoro-1,3-dioxole, perfluoro (2-methylene-4-methyl-1,3-dioxolane), etc.) and the like.

As the fluorine-containing monomer, at least one selected from the group consisting of HFP, PAVE, and FAE is preferable from the viewpoint of excellent melt moldability of the fluorine-containing copolymer A1, flexibility of the fluorine resin layer, and the like.
Examples of PAVE include CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F, and the like. ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”) is preferable.

The _{FAE, CH 2 = CF (CF} 2) 2 F, CH 2 = CF (CF 2) 3 F, CH 2 = CF (CF 2) 4 F, CH 2 = CF (CF 2) 5 F, CH 2 _{= CF (CF 2) 8 F} , CH 2 = CF (CF 2) 2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2) _{5 H, CH 2 = CF (} CF 2) 8 H, CH 2 = CH (CF 2) 2 F, CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 F, CH 2 = _{CH (CF 2) 5 F,} CH 2 = CH (CF 2) 6 F, CH 2 = CH (CF 2) 8 F, CH 2 = CH (CF 2) 2 H, CH 2 = CH (CF 2) 3 _{H, CH 2 = CH (CF} 2) 4 H, CH 2 = CH (CF 2) 5 H, CH 2 = H _{(CF 2) 8} H, and the like.
The _{FAE, CH 2 = CH (CF} 2) q1 X 4 ( although, q1 is 2-6, 2-4 is preferred.) Are _{preferable, 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 is more preferred, and CH ₂ ═CH ( CF ₂ ) ₄ F (hereinafter also referred to as “PFBE”) and CH ₂ ═CH (CF ₂ ) ₂ F (hereinafter also referred to as “PFEE”) are more preferable.

The fluorinated copolymer A1 may further have a unit derived from a non-fluorine monomer (excluding an acid anhydride monomer) in addition to the TFE unit, the unit u2 and the unit u3. .
The non-fluorine monomer is preferably a non-fluorine compound having one polymerizable carbon-carbon double bond, and examples thereof include olefins (ethylene, propylene, 1-butene, etc.), vinyl esters (vinyl acetate, etc.) and the like. It is done. A non-fluorine monomer may be used individually by 1 type, and may use 2 or more types together.

Preferable specific examples of the fluorinated copolymer A1 include the following.
A copolymer having TFE units, NAH units and PPVE units;
A copolymer having TFE units, IAH units and PPVE units;
A copolymer having TFE units, CAH units and PPVE units;
A copolymer having TFE units, IAH units and HFP units;
A copolymer having TFE units, CAH units and HFP units;
A copolymer having a TFE unit, an IAH unit, a PFBE unit, and an ethylene unit;
A copolymer having TFE units, CAH units, PFBE units and ethylene units;
A copolymer having TFE units, IAH units, PFEE units and ethylene units;
A copolymer having TFE units, CAH units, PFEE units, and ethylene units;
Copolymers having TFE units, IAH units, HFP units, PFBE units and ethylene units.
As the fluorine-containing copolymer A1, a copolymer having a TFE unit, a NAH unit, and a PPVE unit is preferable from the viewpoint of good heat resistance.

The preferred ratio of each unit in the case where the fluorine-containing heavy copolymer A1 is composed of a TFE unit, a unit u2 and a unit u3 is as follows.
The proportion of TFE units is preferably from 50 to 99.89 mol%, more preferably from 90 to 99.49 mol%, still more preferably from 95 to 98.95 mol% of all units.
The proportion of the unit u2 is preferably from 0.01 to 5 mol%, more preferably from 0.01 to 3 mol%, still more preferably from 0.05 to 1 mol%, based on all units.
The ratio of the unit u3 is preferably from 0.1 to 49.99 mol%, more preferably from 0.5 to 9.99 mol%, and even more preferably from 1 to 4.95 mol%, based on all units.
When the ratio of each unit is within the above range, the heat resistance, chemical resistance and elastic modulus at high temperature of the fluororesin layer are excellent. When the ratio of the unit u2 is within the above range, the amount of the acid anhydride group in the fluorine-containing copolymer A1 is appropriate, and the adhesiveness is further improved. When the ratio of the unit u3 is within the above range, the fluorine-containing copolymer A1 has excellent melt moldability, and the fluororesin layer has excellent bending resistance.

Preferred proportion of each unit when the fluorinated copolymer A1 comprises TFE units, units u2, units u3 and units derived from non-fluorine monomers, and the units derived from non-fluorine monomers are ethylene units. Is as follows.
The proportion of TFE units is preferably from 25 to 80 mol%, more preferably from 40 to 65 mol%, still more preferably from 45 to 63 mol%, based on all units.
The ratio of the unit u2 is preferably from 0.01 to 5 mol%, more preferably from 0.03 to 3 mol%, still more preferably from 0.05 to 1 mol%, based on all units.
The ratio of the unit u3 is preferably 0.2 to 20 mol%, more preferably 0.5 to 15 mol%, and even more preferably 1 to 12 mol% among all units.
The proportion of ethylene units is preferably 20 to 75 mol%, more preferably 35 to 50 mol%, and still more preferably 37 to 55 mol%, based on all units.
When the content of each unit is within the above range, the chemical resistance of the fluororesin layer is excellent. When the ratio of the unit u2 is within the above range, the amount of the acid anhydride group in the fluorine-containing copolymer A1 is appropriate, and the adhesiveness is further improved. When the ratio of the unit u3 is within the above range, the fluorine-containing copolymer A1 is excellent in melt moldability, and the fluororesin layer is excellent in bending resistance.
The ratio of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluorinated copolymer A1.

The fluorinated copolymer A1 can be produced by a conventional method. For example, the fluorine-containing copolymer A1 can be produced by polymerizing TFE, an acid anhydride monomer, and a fluorine-containing monomer.
In the polymerization of the monomer, it is preferable to use a radical polymerization initiator.
Polymerization methods include bulk polymerization, solution polymerization using organic solvents (fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, etc.), aqueous media and appropriate organic solvents as required. And suspension polymerization methods using an aqueous medium and an emulsion polymerization method using an emulsifier and a solution polymerization method are preferred.

When the fluorine-containing copolymer A1 is produced, the concentration of the acid anhydride monomer during polymerization is preferably 0.01 to 5 mol%, more preferably 0.1 to 3 mol%, based on all monomers. Preferably, 0.1 to 2 mol% is more preferable. When the concentration of the acid anhydride monomer is within the above range, the polymerization rate is moderate. When the concentration of the acid anhydride monomer is too high, the polymerization rate tends to decrease.
As the acid anhydride monomer is consumed in the polymerization, the consumed amount is continuously or intermittently supplied into the polymerization tank, and the concentration of the acid anhydride monomer is maintained within the above range. preferable.

(Metal layer)
The metal layer is a layer derived from the metal foil used in the production method of the present invention. The metal layer may be a metal foil itself or a conductor circuit derived from the metal foil.

  Examples of the metal foil material include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, and aluminum alloy. In semiconductor packages and printed wiring boards, copper foil such as rolled copper foil and electrolytic copper foil is frequently used, and copper foil is also suitable in the present invention.

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.
The surface of the metal foil may be subjected to a surface treatment (coupling agent treatment or the like) for enhancing the adhesion with the adhesive layer.

  Examples of the conductor circuit include those obtained by processing a metal foil into a predetermined pattern by etching or the like, and those formed by electrolytic plating using a metal foil using a semi-additive method (SAP method) or a modified semi-additive method (MSAP method). Can be mentioned.

(Other layers)
As other layers in the laminate, a resin layer other than a specific fluororesin layer (protective layer, adhesive layer, interlayer insulating film, solder resist, coverlay film, etc.), an inorganic layer other than a specific inorganic layer, a fluororesin layer Examples thereof include a metal layer and a fiber reinforced resin layer that are not provided on the surface. The other layer in the laminate may be a layer derived from a layer other than the inorganic layer in the substrate having the inorganic layer used in the production method of the present invention.
The other layer in the laminate may be provided on the surface of the inorganic layer, may be provided on the surface of the fluororesin layer, or may be provided between the fluororesin layer and the metal layer, It may be provided on the surface of the metal layer.
The laminated body may be provided with electronic components (resistors, inductors, capacitors, etc.).

<Method for producing laminate>
In the method for producing a laminate of the present invention, the surface of either or both of the surface of the inorganic layer of the first base material having the inorganic layer and the surface of the fluororesin layer of the second base material having the fluororesin layer is used. In this method, the first base material and the second base material are thermocompression-bonded at a temperature equal to or higher than the melting point of the fluororesin A with the inorganic layer and the fluororesin layer in contact with each other.
In the manufacturing method of the laminated body of this invention, when a 1st base material has only an inorganic layer or a 1st base material has an inorganic layer in both outermost layers, two 1st base materials are used. Thermocompression bonding may be performed by sandwiching the second substrate.
In the manufacturing method of the laminated body of this invention, when a 2nd base material has only a fluororesin layer, after thermocompression-bonding a 1st base material and a 2nd base material, or simultaneously with a press bonding, a fluororesin layer A third base material may be laminated on the surface.

(First base material)
The first substrate has an inorganic layer.
The first substrate may be a single-layer substrate (a glass substrate, a ceramic substrate, a semiconductor substrate, etc.) having only an inorganic layer, and a laminated substrate having an inorganic layer and a layer other than the inorganic layer. It may be.
As a layer other than the inorganic layer, a resin layer (a protective layer, an adhesive layer, an interlayer insulating film, a solder resist, other than a specific fluororesin layer) provided on the surface opposite to the side on which the fluororesin layer is formed. Coverlay film, etc.), inorganic layers other than the specific inorganic layer, metal layers not provided on the surface of the fluororesin layer, fiber reinforced resin layers, and the like.

You may form holes, such as a through hole and a blind hole, in an inorganic layer.
The hole is formed by, for example, a laser processing method or a discharge assist type laser processing method.
The shape of the hole is not particularly limited. For example, when using a CO ₂ laser, the diameter (upper hole diameter) of the opening formed on the surface (first surface) irradiated with the laser light is preferably 40 to 150 μm, more preferably 50 to 100 μm, More preferably, the thickness is 60 to 90 μm. In the case of using a CO ₂ laser, the diameter (the lower hole diameter) of the opening formed on the surface (second surface) opposite to the side irradiated with the laser light is preferably 10 to 60 μm, and more preferably 20 to 50 μm. Preferably, 30 to 40 μm is more preferable. Moreover, when using a UV laser, 1-30 micrometers is preferable, as for an upper hole diameter, 5-20 micrometers is more preferable, and 10-15 micrometers is further more preferable. When using a UV laser, the diameter of the lower hole is preferably 1 to 10 μm, more preferably 1 to 5 μm, and further preferably 1 to 3 μm.

(Second base material)
The second substrate has a fluororesin layer.
The second substrate may be a single layer substrate (fluorine resin film or the like) having only a fluororesin layer, and a laminate substrate (copper-clad laminate) having a fluororesin layer and a layer other than the fluororesin layer. Etc.).
As a layer other than the fluororesin, a metal layer provided on the surface opposite to the side in contact with the inorganic layer, a resin layer other than the specific fluororesin layer (protective layer, adhesive layer, interlayer insulating film, solder resist, Coverlay film, etc.), inorganic layers other than specific inorganic layers, fiber reinforced resin layers, and the like. As the layer other than the fluororesin, a metal layer made of a metal foil is preferable because the laminate is used as a substrate for a semiconductor package or a printed wiring board.

The second substrate can be produced, for example, by the following method I or method II.
Method I: A method in which a liquid composition in which a fluororesin powder containing fluororesin A is dispersed in a liquid medium is applied to the surface of a substrate to be coated, dried, and then fired.
Method II: A method of obtaining a fluororesin film by molding a resin composition containing fluororesin A.

(Liquid composition)
The liquid composition includes a specific fluororesin powder, a surfactant, and a liquid medium.
The liquid composition is also referred to as an inorganic filler, a resin powder other than a specific fluororesin powder, and a resin that can be dissolved in a liquid medium (hereinafter also referred to as “soluble resin”) as long as the effects of the present invention are not impaired. ), Additives other than the surfactant may be included.

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, cyclohexanone, cyclopentanone, etc.), glycol ether (ethylene glycol monoisopropyl ether, etc.), cellosolve ( Methyl cellosolve, ethyl cellosolve, etc.). 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 fluororesin powder.

The fluororesin powder is made of a powder material containing the fluororesin A.
The powder material is preferably mainly composed of the fluororesin A. If the fluororesin A is the main component, the relative dielectric constant and dielectric loss tangent of the fluororesin layer can be further reduced. Moreover, it is easy to obtain a fluororesin powder having a high bulk density. The higher the bulk density of the fluororesin powder, the better the handling properties. The powder material mainly composed of the fluororesin A means that the ratio of the fluororesin A in the powder material is 80% by mass or more. The proportion of the fluororesin A in the powder material is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

  The D50 of the fluororesin powder is preferably 0.3 to 6.0 μm, more preferably 0.4 to 5.0 μm, still more preferably 0.5 to 4.5 μm, and even more preferably 0.7 to 4.0 μm. 1.0 to 3.5 μm is particularly preferable. If D50 of the fluororesin powder is not less than the lower limit of the above range, the fluororesin powder has sufficient fluidity and is easy to handle. If D50 of fluororesin powder is below the upper limit of the said range, it will be excellent in the dispersibility to the liquid medium of fluororesin powder. Moreover, the filling rate of the fluororesin 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.

  The D90 of the fluororesin powder is preferably 8.0 μm or less, more preferably 6.0 μm or less, and even more preferably 1.5 to 5.0 μm. If D90 of fluororesin powder is below the upper limit of the said range, it will be excellent in the dispersibility to the liquid medium of fluororesin powder. D90 of the fluororesin powder is preferably close to D50 from the viewpoint of excellent uniformity of the fluororesin layer.

The bulk density of the fluororesin 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 packing bulk density of the fluororesin 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.
When 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 fluororesin powder is further improved. Moreover, the filling rate of the fluororesin powder into 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 powder material may further contain components other than the fluororesin A as necessary, as long as the effects of the present invention are not impaired. Examples of components other than the fluororesin A include resins other than the fluororesin A, inorganic fillers, rubbers, and the like. Examples of the resin other than the fluororesin A include aromatic polyester, polyamideimide, thermoplastic polyimide, polyphenylene ether, polyphenylene oxide, and the like.

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

The surfactant improves the dispersion stability of the fluororesin powder in the liquid medium. In addition, at the interface between the inorganic layer and the fluororesin layer, the surface tension of the inorganic layer and the surface tension of the fluororesin A are relaxed to improve the adhesion between the inorganic layer and the fluororesin layer.
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. As the surfactant, a nonionic surfactant is preferable. Surfactant may be used individually by 1 type and may use 2 or more types together.

As the surfactant, a fluorine-based surfactant having a fluorine-containing group and a hydrophilic group is preferable. By using a fluorosurfactant, the surface tension of the liquid medium is reduced, the wettability to the surface of the fluororesin powder is improved, and the dispersibility of the fluororesin powder is improved. Adsorbed on the surface, the hydrophilic group extends into the liquid medium, and the steric hindrance of the hydrophilic group prevents aggregation of the fluororesin powder, thereby further improving the dispersion stability. The following are mentioned as a fluorine-type surfactant.
Aftergent M series, Aftergent F series, Aftergent G series, Aftergent PD series, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 730FL, Aftergent 730LM, Aftergent 610FM Tangent 601AD, tangent 601ADH2, tangent 602A, tangent 650AC, tangent 681.
Surflon series (Surflon S-386 etc.) manufactured by AGC Seimi Chemical Co., Ltd.
DIC's Mega Fuck Series (Mega Fuck F-553, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-557, Mega Fuck F-559, Mega Fuck F-562, Mega Fuck F-565, etc. ).
Unidyne series (Unidyne DS-403N etc.) manufactured by Daikin Industries.

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 (except for fluorinated copolymer A), thermosetting polyimide, Examples thereof include polyamic acid which is a precursor.
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.

  5-60 mass% is preferable, as for the ratio of the fluororesin powder in a liquid composition, 30-50 mass% is more preferable, and 35-45 mass% is further more preferable. If the ratio of the fluororesin powder is not less 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 fluororesin powder is not more than the upper limit of the above range, the fluororesin powder is easily dispersed uniformly in the liquid composition, and the fluororesin layer is excellent in mechanical strength.

  The ratio of the liquid medium in the liquid composition is preferably 15 to 65% by mass, and more preferably 25 to 50 parts by mass. If the ratio of a liquid medium exists in the said range, the applicability | paintability of a liquid composition will become favorable. If the ratio of the liquid medium is equal to or less than the upper limit of the above range, the amount of the liquid medium used is small, so that the appearance defect of the fluororesin layer due to poor drying hardly occurs.

  0.1-30 mass% is preferable, as for the ratio of surfactant in a liquid composition, 3-20 mass parts is more preferable, and 5-10 mass parts is further more preferable. When the ratio of the surfactant is not less than the lower limit of the above range, the fluororesin 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.

  When a liquid composition contains a soluble resin, 1-50 mass% is preferable and, as for the ratio of the soluble resin in a liquid composition, 5-30 mass parts 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.

(Production of second substrate)
In Method I, the liquid composition is applied to the surface of the substrate to be applied.
Examples of the base material to be applied include metal foil, resin films other than fluororesin films containing a specific fluororesin, inorganic base materials, fiber reinforced resin base materials, etc., and the laminate as a substrate for semiconductor packages and printed wiring boards From the point of use, metal foil is preferable.

  As coating methods, 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 Mayer bar method, slot die coating Law.

In Method I, the substrate to be coated on which the liquid composition is applied is dried and baked to melt the fluororesin powder and form a fluororesin layer.
In drying, it is not 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.
The drying temperature is preferably 50 to 150 ° C, more preferably 80 to 100 ° C. 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.

The baking may be performed simultaneously with the application of the paint, may be after the application of the paint, or the application and baking of the paint may be repeated.
The firing temperature is preferably equal to or higher than the melting point of the fluororesin A, more preferably 180 to 400 ° C, and further preferably 200 to 360 ° C. The firing temperature is the temperature of the atmosphere.
The firing time is preferably 0.5 to 30 minutes, and more preferably 1 to 10 minutes.

In Method II, the fluororesin film can be produced by molding a resin composition containing fluororesin A into a film by a known melt molding method (extrusion molding method or the like). The resin composition may further contain a component other than the fluororesin A as necessary, as long as the effects of the present invention are not impaired. Examples of components other than the fluororesin A include resins other than the fluororesin A, inorganic fillers, rubbers, various additives, and the like.
The fluororesin film may be produced by a casting method using a liquid composition.

(Third substrate)
Examples of the third substrate include a metal foil, a resin film other than a fluororesin film containing a specific fluororesin, an inorganic substrate, a fiber reinforced resin substrate, and the like. As the third base material, a metal foil is preferable because the laminate is used as a substrate for a semiconductor package or a printed wiring board.

(surface treatment)
By subjecting the surface of the inorganic layer of the base material to be surface-treated to either or both of the surface of the inorganic layer of the first base material and the surface of the fluororesin layer of the second base material, the inorganic layer And the adhesion between the fluororesin layer is further improved. When the third substrate is used, the surface of the third substrate may be surface-treated.
Examples of the surface treatment include wet treatment, plasma treatment (atmospheric pressure plasma treatment, vacuum plasma treatment), corona treatment, UV ozone treatment, and excimer treatment.

As the surface treatment for the inorganic layer of the first substrate, wet treatment or plasma treatment is preferred, and wet treatment is particularly preferred from the viewpoint of further excellent adhesion between the inorganic layer and the fluororesin layer. In particular, when the inorganic layer has pores, wet treatment is performed on the surface of the inorganic layer, so that a fluororesin A can sufficiently enter the pores, and a laminate in which the fluororesin A is not lost in the pores can be manufactured.
As the surface treatment for the fluororesin layer of the second substrate, plasma treatment is preferable, and vacuum plasma treatment is particularly preferable from the viewpoint that the adhesion between the inorganic layer and the fluororesin layer is further excellent.
In view of further excellent adhesion between the inorganic layer and the fluororesin layer, it is preferable to wet-treat the surface of the inorganic layer and plasma-treat the surface of the fluororesin layer.

  The wet treatment is a treatment that brings a wet treatment liquid into contact with the surface of the inorganic layer and exhibits one or more of the following effects. Effects include surface cleaning, surface modification, and surface roughening. In the case where pores are formed in the inorganic layer, wet treatment is preferably used because it is difficult to activate the inner wall surface of the pores by plasma treatment or ultraviolet irradiation. In addition, since the transmission loss in an inorganic layer will generate | occur | produce when it roughens too much, it is preferable to select the wet process from which arithmetic mean roughness Ra becomes 1 micrometer or less about a roughening process.

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

  Surface modification is intended to introduce reactive functional groups (silanol groups, amino groups, hydrocarbon groups, etc.) that can chemically bond to the adhesive functional groups of the fluororesin layer into the surface of the inorganic layer during thermocompression bonding. Done. The surface modification is performed by etching the surface of the inorganic layer, attaching a surface treatment agent to the surface of the inorganic layer, or the like. Examples of the wet treatment liquid used for the surface modification include known glass etching liquids (alkali aqueous solution, hydrofluoric acid aqueous solution, etc.) and liquids containing surface treatment agents (silane coupling agents, cationic polymers, chelating agents, etc.).

The etching solution used for the surface modification may be appropriately selected from known etching solutions according to the material of the inorganic layer. Examples of the etching solution include a solution containing hydrofluoric acid, sulfuric acid, nitric acid, perchloric acid, and the like, a solution containing an alkali such as sodium hydroxide, potassium hydroxide, and the like. When the material of the inorganic layer is glass, an alkaline aqueous solution having a pH of 11 to 14 in which the surface is not excessively roughened is preferable.
The etching solution used for surface modification preferably contains a chelating agent. When the etching solution contains a chelating agent, the chelating agent is coordinated on the surface of the inorganic layer after the wet treatment, and the adhesion between the inorganic layer and the fluororesin layer is further improved. The ratio of the chelating agent in the etching solution is preferably 0.1% by mass or more. Examples of the chelating agent used in the etching solution include an alkaline chelating agent described in JP-A-2006-60862.

Examples of the silane coupling agent used for the surface modification include aminosilane, mercaptosilane, vinyl silane, epoxy silane, methacryl silane, ureido silane, and alkyl silane.
Cationic polymers used for surface modification include amine-type cationic polymers such as polyethyleneimine, polyallylamine, dicyandiamide-diethylenetriamine condensate, polydiallyldimethylammonium chloride, poly (dimethylaminoethyl acrylate methyl chloride quaternary salt), and poly (dimethyl). Quaternary ammonium type cationic polymers such as aminoethyl methacrylate methyl chloride quaternary salt), trimethylammonium alkylacrylamide polymer salt, dimethylamine epichlorohydrin condensate salt and the like.
Chelating agents used for surface modification include gluconic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethanediphosphonic acid, nitrilotrismethylenephosphonic acid, gluconic acid, ethylenediaminetetraacetic acid, citric acid, tartaric acid, malic acid Succinic acid, malonic acid, oxalic acid and the like.

  The surface roughening is a process for roughening the surface of the inorganic layer and increasing the adhesiveness by an anchor effect. Examples of the wet treatment liquid used for surface roughening include known glass etching liquids (alkali aqueous solution, hydrofluoric acid aqueous solution, etc.).

Examples of the vacuum plasma processing method include a high frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate method, a remote plasma method, and an ICP type high density plasma method. Examples of the gas used for the vacuum plasma treatment include oxygen gas, nitrogen gas, rare gas (such as argon gas), hydrogen gas, and ammonia gas, and rare gas or nitrogen gas is preferable. One type of gas may be used alone, or two or more types may be mixed and used. For example, argon gas may be 100% by volume, hydrogen gas / nitrogen gas may be a mixed gas of 70/30 (volume ratio), or hydrogen gas / nitrogen gas / argon gas may be 35/15/50 (volume ratio). A mixed gas of
The atmosphere of the vacuum 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. 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, the surface of the fluororesin layer can be sufficiently roughened.
The gas flow rate, the degree of vacuum, and the processing time in the vacuum plasma processing are appropriately selected depending on the composition of the surface-treated fluororesin layer and the structure of the vacuum plasma processing apparatus.

The arithmetic average roughness Ra of the surface of the inorganic layer after the surface treatment is preferably 1.0 μm or less, more preferably 0.5 μm or less, and further preferably 0.001 to 0.1 μm. When the arithmetic average roughness Ra of the surface of the inorganic layer is not less than the lower limit of the above range, the surface of the inorganic layer is sufficiently roughened, and the adhesion between the inorganic layer and the fluororesin layer is further improved. If the arithmetic average roughness Ra of the surface of the inorganic layer is not more than the upper limit of the above range, a decrease in mechanical strength of the inorganic layer can be suppressed.
In addition, Ra (AFM) on the surface of the inorganic layer after the surface treatment is also preferably 1.0 μm or less, more preferably 0.5 μm or less, and further preferably 0.001 to 0.1 μm. A preferable reason is the same as the arithmetic average roughness Ra.
Ra (AFM) of the surface of the inorganic layer after the surface treatment can be measured by the method described in the examples described later.

(Thermo-compression bonding)
The first base material and the second base material are thermocompression-bonded at a temperature equal to or higher than the melting point of the fluororesin A in a state where the inorganic layer and the fluororesin layer are in contact with each other.
When the first substrate has only an inorganic layer, or the first substrate has inorganic layers on both outermost layers, the first substrate is sandwiched between two second substrates and thermocompression bonded. May be.
When the second base material has only the fluororesin layer, the third base material is thermocompression bonded to the surface of the fluororesin layer after thermocompression bonding of the first base material and the second base material or simultaneously with the pressure bonding. May be.
Examples of thermocompression bonding include hot pressing and thermal lamination.

  The temperature at the time of pressure bonding is not less than the melting point of the fluororesin A, preferably 10 ° C. or more higher than the melting point, more preferably 20 ° C. or more higher than the melting point, and more preferably 40 ° C. or more higher than the melting point. It is preferable that the temperature at the time of pressure bonding does not exceed a temperature 3 ° C. higher than the melting point. If the temperature at the time of pressure bonding is within the above range, the inorganic layer and the fluororesin layer can be sufficiently bonded while suppressing the thermal deterioration of the fluororesin A. The temperature at the time of crimping is the temperature of the hot platen.

  The pressure at the time of pressure bonding is preferably 0.2 MPa or more, more preferably 0.5 MPa or more, and further preferably 1.0 MPa or more. The pressure during pressure bonding is preferably 10.0 MPa or less. If the pressure at the time of pressure bonding is within the above range, the fluororesin layer and the metal foil can be sufficiently bonded without damaging the inorganic layer. In addition, it is possible to fill the pores of the inorganic layer with resin.

The thermocompression bonding is preferably performed in a vacuum atmosphere. The degree of vacuum is preferably 100 kPa or less, more preferably 50 kPa or less, and further preferably 20 kPa or less. If the degree of vacuum is within the above range, it is possible to suppress bubbles from entering the respective interfaces of the fluororesin layer, the inorganic layer and the metal layer constituting the laminate, and to suppress deterioration due to oxidation.
Moreover, it is preferable to raise the temperature after reaching the vacuum degree. If the temperature is raised before reaching the degree of vacuum, the fluororesin layer is compressed in a softened state, that is, with a certain degree of fluidity and adhesion, which causes bubbles.

(Mechanism of action)
In the manufacturing method of the laminated body of this invention demonstrated above, since the 1st base material which has an inorganic layer is used, the laminated body excellent in dimensional stability can be manufactured.
Moreover, in the manufacturing method of the laminated body of this invention, since the 2nd base material which has the fluororesin layer containing the fluororesin A is used, the laminated body which is excellent in an electrical property can be manufactured.
Moreover, in the manufacturing method of the laminated body of this invention, either one or both of the surface of the inorganic layer of a 1st base material and the surface of the fluororesin layer of a 2nd base material is surface-treated, 1st In order for the base material and the second base material to be thermocompression bonded at a temperature equal to or higher than the melting point of the fluororesin in a state where the inorganic layer and the fluororesin layer are in contact, a laminate having excellent adhesion between the inorganic layer and the fluororesin layer Can be manufactured.
In particular, when the inorganic layer has pores, wet treatment is performed on the surface of the inorganic layer, so that a fluororesin A can sufficiently enter the pores, and a laminate in which the fluororesin A is not lost in the pores can be manufactured.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1 to 10 are examples, and examples 11 to 16 are comparative examples.

(Ratio of each unit in the fluorinated copolymer)
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 fluorine-containing copolymer 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 fluorine-containing copolymer appears at 1778 cm ⁻¹ . The absorbance at this absorption peak was measured, and the ratio of NAH units in the fluorinated copolymer was determined using a molar absorption coefficient of NAH 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 fluorine-containing copolymer was raised at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value (° C. ) As the melting point.

(MFR)
Using a melt indexer (manufactured by Techno Seven Co., Ltd.), measuring the mass (g) of the fluorine-containing copolymer 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 for 10 minutes, MFR and did.

(Relative permittivity)
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. The value obtained at 1 MHz using YSY-243-100RHO manufactured by Kikai Co., Ltd. was defined as the relative dielectric constant. Further, in a higher frequency band, measurement was performed at a frequency of 20 GHz by an SPDR (split post dielectric resonator) method in an environment within a range of 23 ° C. ± 2 ° C. and 50 ± 5% RH.

(Fluorine-containing copolymer 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 fluorine-containing copolymer was put into the top sieve and sieved with a shaker for 30 minutes. The mass of the fluorinated copolymer 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 the fluorine-containing amount. It was set as D50 of the copolymer.

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

(Resistivity)
The resistivity of the substrate at 25 ° C. was measured using a resistivity meter (Mitsubishi Chemical Analytech, Loresta MCP-T250).

(Ra (AFM))
Ra (AFM) of the surface of the inorganic layer after the surface treatment was calculated by measuring surface irregularities using AFM “Cypher S” manufactured by Oxford Instruments.
Probe: AC55TS (tip R <7 nm, spring constant 85 N / m),
Measurement mode: AC-Air,
Scan Area: 30 μm square,
Scan Rate: 1Hz,
Scanpoint: 256 × 256.
Ra (AFM) was defined as the average of the difference between the height at each scanpoint and the average height.

(Peel test)
A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the laminate. The fluororesin layer and the inorganic 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 at 90 ° at a pulling speed of 50 mm / min, the maximum load is peel strength (N / cm ).

(Production of fluorinated copolymer A)
Using TFE, NAH (manufactured by Hitachi Chemical Co., Ltd., Himic Acid Anhydride), PPVE (manufactured by Asahi Glass Co., Ltd.), the fluorine-containing copolymer A1-1 was prepared by the procedure described in paragraph [0123] of International Publication No. Manufactured. The ratio of each unit in the fluorinated copolymer A1-1 was NAH unit / TFE unit / PPVE unit = 0.1 / 97.9 / 2.0 (mol%). The melting point of the fluorinated copolymer A1-1 is 300 ° C., the MFR is 17.6 g / 10 min, the relative dielectric constant is 2.1 (measurement frequency: 1 MHz), and the fluorine content is 75 mass%. The content of the adhesive functional group with respect to 1 × 10 ⁶ main chain carbon atoms of the fluorinated copolymer A1-1 was 1000, and D50 was 1554 μm.

(Manufacture of fluororesin film)
Using a 65 mmφ single screw extruder having a 750 mm wide coat hanger die, the fluorocopolymer A1-1 was extruded into a film at a die temperature of 340 ° C. to obtain a fluororesin film having a thickness of 50 μm.

(Manufacture of fluororesin powder)
Fluorine-containing copolymer A1-1 was pulverized by 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 and processing speed: 1 kg / hour. Resin powder X-1 was obtained. D50 of the fluororesin powder X-1 was 2.58 μm, and D90 was 7.1 μm. The loose filling bulk density of the fluororesin powder X-1 was 0.278 g / mL, and the dense filling bulk density was 0.328 g / mL.

(Preparation of liquid composition)
To 120 g of resin powder X-1, 9 g of a nonionic surfactant (manufactured by Neos, Footage 710FL) and 234 g of methyl ethyl ketone are gradually added, and a lab stirrer (manufactured by Yamato Kagaku, model: LT-500) is added. The mixture was stirred for 60 minutes to obtain a liquid composition.

(Polyimide film)
As a polyimide film, Ube Industries, Upilex (registered trademark) 125S, thickness: 125 μm was prepared.

(Example 1)
As a glass substrate, an alkali-free glass plate (manufactured by Asahi Glass Co., Ltd., EN-A1, thickness: 0.3 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)) was prepared.
The glass substrate was immersed in a 10% by mass aqueous sodium hydroxide solution at 23 ° C. and wet-treated while being irradiated with ultrasonic waves. The liquid temperature gradually increased by ultrasonic irradiation, and became 45 ° C. after 1 hour. After immersion for 1 hour, the glass substrate was pulled up from the solution. The glass substrate was thoroughly washed with pure water, dried by air blow, and a wet-treated glass substrate was obtained. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.

  A wet-treated glass substrate, a fluororesin film, and a polyimide film are stacked in this order and placed in a vacuum press machine. Vacuum bonding was performed under conditions for 10 minutes to obtain a laminate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 2)
As a glass substrate, a quartz glass plate (manufactured by Asahi Glass Co., Ltd., thickness: 0.7 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)) was prepared.
The glass substrate was dipped in a glass cleaning solution at 23 ° C. (Yokohama Yushi Kogyo Co., Ltd., stock solution of glass cleaning liquid semi-clean GE-5, pH: 13), and wet-treated while irradiating ultrasonic waves. The liquid temperature gradually increased by ultrasonic irradiation, and became 45 ° C. after 1 hour. After immersion for 1 hour, the glass substrate was pulled up from the solution. The glass substrate was thoroughly washed with pure water, dried by air blow, and a wet-treated glass substrate was obtained. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.

  A wet-treated glass substrate, a fluororesin film, and a polyimide film are stacked in this order and put into a vacuum press machine. The degree of vacuum is 10 kPa, the temperature at the time of pressure bonding is 340 ° C., the pressure at the time of pressure bonding is 2.0 MPa, the hold: Vacuum bonding was performed under conditions for 10 minutes to obtain a laminate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 3)
Except for changing the glass substrate to an alkali-free glass plate (Asahi Glass Co., Ltd., EN-A1, thickness: 0.3 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)) A glass substrate wet-treated in the same manner as in No. 2 was obtained. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 2 except that the wet-treated glass substrate of Example 3 was used. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 4)
Other than changing the glass substrate to a chemically strengthened glass plate (Asahi Glass Co., Ltd., Dragon Trail (registered trademark), thickness: 0.7 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)) Obtained a glass substrate wet-treated in the same manner as in Example 2. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 2 except that the wet-treated glass substrate of Example 4 was used. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 5)
Wet treatment was carried out in the same manner as in Example 2 except that the glass substrate was changed to a soda lime glass plate (thickness: 0.7 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)). A glass substrate was obtained. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 2 except that the wet-treated glass substrate of Example 5 was used. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 6)
The alkali-free glass plate was immersed in an aqueous solution of 100 mg / L polyethyleneimine (mass average molecular weight: 600) for 10 seconds, washed with water and dried to obtain a wet-treated glass substrate. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 1 except that the wet-treated glass substrate of Example 6 was used. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 7)
The alkali-free glass plate was immersed in an aqueous solution of 100 mg / L polyethyleneimine (mass average molecular weight: 10,000) for 10 seconds, then washed with water and dried to obtain a wet-treated glass substrate. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 1 except that the wet-treated glass substrate of Example 7 was used. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 8)
The alkali-free glass plate was immersed in a 10 mM aqueous solution of hydroxyethanediphosphonic acid for 1 minute, then washed with water and dried to obtain a wet-treated glass substrate. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.
A laminate was obtained in the same manner as in Example 1 except that the glass substrate was changed to the wet-treated glass substrate of Example 8. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 9)
A wet-treated glass substrate was obtained in the same manner as in Example 2. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.

The liquid composition was applied to the roughened surface of copper foil (Fukuda Metal Foil Powder Co., Ltd., CF-T4X-SV, thickness: 12 μm), dried at 100 ° C. for 15 minutes in a nitrogen atmosphere, and 350 ° C. Heated for 15 minutes and slowly cooled. A copper clad laminate having a fluororesin layer having a thickness of 5 μm was obtained.
The surface of the fluororesin layer of the copper clad laminate was plasma treated. AP-1000 manufactured by NORDSON MARCH was used as the plasma processing apparatus. 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 vacuum-clad copper-clad laminate and the wet-treated glass substrate are put into a vacuum press machine so that the fluororesin layer and the glass substrate are in contact with each other. The degree of vacuum is 10 kPa, and the temperature during pressure bonding : 340 ° C., pressure during pressure bonding: 2.0 MPa, hold: vacuum pressure bonding under conditions of 10 minutes to obtain a laminate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 10)
100 mm × 100 mm area in the center of an alkali-free glass plate (Asahi Glass Co., Ltd., EN-A1, diameter: 200 mm, thickness: 0.3 mm, resistivity at 25 ° C .: outside measurement range (10 ⁵ Ω · cm or more)) In addition, 100,000 through holes having an upper hole diameter of 85 μm and a lower hole diameter of 40 μm were formed in a square lattice shape.
A wet-treated glass substrate was obtained in the same manner as in Example 1 except that the glass substrate was changed to a non-alkali glass plate having holes. Table 1 shows the Ra (AFM) of the surface of the wet-treated glass substrate.

The polyimide film, fluororesin film, wet-treated glass substrate, fluororesin film, and polyimide film are put into a vacuum press machine in this order, and the degree of vacuum is 10 kPa, the temperature during pressure bonding is 340 ° C., the pressure during pressure bonding : 2.0 MPa, hold: vacuum press-bonded for 10 minutes to obtain a laminate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.
Moreover, the laminated body after a peeling test was cleaved, and the cross section was observed with a scanning electron microscope (SEM). The SEM photograph of the cross section of the hole part of a glass base material is shown in FIG. The left side of the SEM photograph is a glass substrate, and the right side is a fluororesin. No peeling of the fluororesin from the holes in the glass substrate was visible.

(Examples 11-14)
A laminate was obtained in the same manner as in Examples 2 to 5 except that the surface of the glass substrate was not wet-treated. Table 1 shows the Ra (AFM) of the surface of the glass substrate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 15)
A laminate was obtained in the same manner as in Example 9, except that the surface of the glass substrate was not wet-treated and the surface of the fluororesin layer of the copper-clad laminate was not vacuum plasma treated. Table 1 shows the Ra (AFM) of the surface of the glass substrate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.

(Example 16)
A laminate was obtained in the same manner as in Example 10 except that the surface of the glass substrate was not wet-treated. Table 1 shows the Ra (AFM) of the surface of the glass substrate. Table 1 shows the peel strength at the interface between the fluororesin layer and the inorganic layer of the laminate.
Moreover, the laminated body after a peeling test was cleaved, and the cross section was observed with SEM. The SEM photograph of the cross section of the hole part of the glass substrate is shown in FIG. The left side of the SEM photograph is a glass substrate, and the right side is a fluororesin. The peeling of the fluororesin from the hole of the glass substrate was observed occasionally.

  The laminate obtained by the production method of the present invention is useful as a substrate used for a semiconductor package or a printed wiring board.

11 laminates,
12 laminates,
13 laminates,
14 laminates,
20 inorganic layer,
22 fluorine resin layer,
24 Metal layer.

Claims (14)

It is a method for producing a laminate having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more and a fluororesin layer containing the following fluororesin provided on the surface of the inorganic layer.
Surface-treating one or both of the surface of the inorganic layer of the first base material having the inorganic layer and the surface of the fluororesin layer of the second base material having the fluororesin layer,
The manufacturing method of a laminated body which thermocompression-bonds the said 1st base material and the said 2nd base material above the melting | fusing point of the said fluororesin in the state which the said inorganic layer and the said fluororesin layer contacted.
Fluororesin:
A fluororesin 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 and is melt-moldable.   The manufacturing method of the laminated body of Claim 1 which plasma-processes any one or both of the surface of the said inorganic layer and the surface of the said fluororesin layer.   The manufacturing method of the laminated body of Claim 1 which wet-processes the surface of the said inorganic layer.   The manufacturing method of the laminated body of Claim 1 which wet-processes the surface of the said inorganic layer, and plasma-processes the surface of the said fluororesin layer.   The lamination according to any one of claims 1 to 4, wherein the first base material and the second base material are thermocompression bonded at a pressure equal to or higher than the melting point of the fluororesin and equal to or higher than 0.2 MPa. Body manufacturing method.   The manufacturing method of the laminated body as described in any one of Claims 1-5 whose said fluororesin is a fluorine-containing copolymer which has a unit based on tetrafluoroethylene. Surface treatment of the inorganic layer;
The manufacturing method of the laminated body as described in any one of Claims 1-6 whose arithmetic mean roughness Ra of the surface of the said inorganic layer surface-treated is 1.0 micrometer or less.   The manufacturing method of the laminated body as described in any one of Claims 1-7 whose material of the said inorganic layer is glass, ceramics, or a semiconductor. The first substrate has only the inorganic layer, or the first substrate has the inorganic layer on both outermost layers;
The manufacturing method of the laminated body as described in any one of Claims 1-8 which pinches | interposes the said 1st base material between the said 2nd base materials of 2 sheets, and thermocompression-bonds. The second base material has only the fluororesin layer,
The metal foil is laminated on the surface of the fluororesin layer after thermocompression bonding or simultaneously press-bonding the first base material and the second base material, according to any one of claims 1 to 9. A manufacturing method of a layered product.   The manufacturing method of the laminated body as described in any one of Claims 1-9 in which a said 2nd base material further has a metal layer which consists of metal foil.   The manufacturing method of the laminated body as described in any one of Claims 1-11 in which the hole is formed in the said inorganic layer. A first base material having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more and a second base material having a fluororesin layer are in contact with the inorganic layer and the fluororesin layer. It is a method for producing the first base material used when thermocompression bonding in a state,
The manufacturing method of the 1st base material which wet-processes or plasma-processes the surface of the said inorganic layer of a said 1st base material. A first base material having an inorganic layer having a resistivity at 25 ° C. of 10 ² Ω · cm or more, and a second base material having a fluororesin layer containing the following fluororesin, the inorganic layer and the fluororesin A method for producing the second base material used when thermocompression bonding in a state where the layer is in contact with the layer;
A method for producing a second substrate, wherein the surface of the fluororesin layer of the second substrate is subjected to plasma treatment.
Fluororesin:
A fluororesin 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 and is melt-moldable.