JP2019181803A - Laminate and manufacturing method thereof, application liquid, manufacturing method of printed circuit board - Google Patents

Abstract

To provide a laminate which is excellent in electrical characteristics, adaptable to a frequency in a high frequency band and has a metal layer hardly oxidized when manufactured and excellent adhesion between a cured material layer; and the metal layer, a prepreg or the like even without using a special high temperature apparatus when manufactured, and a manufacturing method of the laminate, and to provide application liquid used for manufacturing the laminate and a manufacturing method of a printed circuit board.SOLUTION: The laminate is provided that comprises: a cured-material layer, the cured-material including cured fluorine resin; and a metal layer which is provided on one surface or both surfaces of the cured-material layer and of which the surface contacting the cured-material layer has a surface roughness Rz of 4.5 μm or less. Further, the laminate has a fiber-reinforced resin layer joined to the surface of the cured-material layer, the surface being opposite side of the cured-metal layer. In the manufacturing method of the printed circuit board, a pattern circuit is formed by etching the metal layer of the laminate to provide a printed circuit board.SELECTED DRAWING: None

Description

  The present invention relates to a laminate, a method for producing the same, a coating solution, and a method for producing a printed circuit board.

  In recent years, the demand for various printed circuit boards has increased with the reduction in weight, size and density of electronic products. As the printed board, a circuit board is formed by laminating a metal foil on an insulating layer made of an insulating material and patterning the metal foil.

  The printed circuit board is required to have excellent electrical characteristics (such as a low dielectric constant) corresponding to a frequency in the high frequency band. As a material having a low dielectric constant and useful for a printed circuit board, resin powder containing a fluororesin having a functional group such as a carbonyl group-containing group and a melting point of 260 ° C. or more has been proposed (Patent Documents 1 and 2).

International Publication No. 2016/017801 International Publication No. 2018/16644

  However, when using a resin powder containing a fluororesin having a melting point of 260 ° C. or higher as in Patent Document 1, it is usually necessary to fire at 260 ° C. or higher (melting point or higher) when forming the insulating layer. Therefore, there is a problem that the facilities that can be handled are limited and the copper foil is easily oxidized and deteriorated by firing. When the firing temperature is lowered, it is difficult to form a uniform insulating layer, and the adhesion between the insulating layer and the metal foil is deteriorated.

  In addition, when a prepreg or the like is bonded to the opposite side of the metal foil in the insulating layer by hot pressing, the hot pressing temperature is usually set lower than the heat resistant temperature of the prepreg or the like. The heat resistant temperature of prepreg and the like is generally lower than 260 ° C. Therefore, when a fluororesin having a melting point of 260 ° C. or higher is used, the fluororesin is not sufficiently melted and it is difficult to obtain excellent adhesion.

  The present invention is excellent in electrical characteristics, can cope with high-frequency frequencies, the metal layer is difficult to oxidize during manufacturing, and can adhere to the cured product layer and the metal layer, prepreg, etc. without using special high-temperature equipment. An object of the present invention is to provide an excellent laminate, a method for producing the laminate, a coating solution used for producing the laminate, and a method for producing a printed circuit board.

The present invention has the following configuration.
[1] A surface roughness Rz of a cured product layer made of a cured product of a resin material containing a curable fluororesin and a surface in contact with the cured product layer provided on one side or both sides of the cured product layer is 4.5 μm. A laminate comprising the following metal layer.
[2] The laminate according to [1], wherein the cured product layer has a water vapor transmission coefficient of 20 g · mm / m ² · day or less.
[3] The laminate according to [1] or [2], wherein the curable fluororesin includes a fluoropolymer having a unit represented by the following formula U1.

(In the formula U1, X ¹ and X ² are each independently a hydrogen atom or a fluorine atom. Q ¹ is a single bond or an etheric oxygen atom. R ^f1 is a fluoroalkylene group, or It is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, Z ¹ is NR ¹ NR ² H, or NR ³ OR ^4. R ¹ , R ² , R ³ , R ⁴ is each independently a hydrogen atom or an alkyl group.)
[4] At least a part of the unit represented by the formula U1 is — [CF ₂ —CF (O (CF ₂ ) ₃ CONHNH ₂ )] — or — [CF ₂ —CF (O (CF ₂ ) ₃ CONHOH )-, The laminate of [3].
[5] The laminate according to [3] or [4], wherein the fluoropolymer further has a unit based on fluoroethylene.
[6] The laminate according to any one of [3] to [5], wherein the fluoropolymer further has a unit represented by the following formula U2 (excluding a unit based on fluoroethylene).
^{- [CX 3 X 4 -CY 1} Y 2] - ··· formula U2
(However, in the formula U2, ^{X 3} and ^{X 4} each independently represent a hydrogen atom, .Y ¹ is a fluorine atom or a chlorine atom, .Y ² is a hydrogen atom, a fluorine atom or a chlorine atom, hydrogen An atom, a fluoroalkyl group, a fluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, a fluoroalkoxy group, or a fluoro having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms An alkoxy group.)
[7] The laminate according to any one of [3] to [6], wherein the fluoropolymer further has a unit represented by the following formula U3.

(In the formula U3, X ⁵ , X ⁶ and X ⁷ are each independently a fluorine atom or a hydrogen atom, two Q ² are each independently a single bond or an etheric oxygen atom, and R ^f2 is the number of carbon atoms. 1-6 fluoroalkylene groups, or C2-C25 fluoroalkylene groups having an etheric oxygen atom between carbon-carbon atoms.)
[8] The content of the group represented by -COZ ¹ of the fluoropolymer in is a 0.01~4.0mmol / g, [3] one of the laminate to [7].
[9] Any of [1] to [8], wherein the resin material further includes at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin curing agent. Such a laminate.
[10] The laminate according to any one of [1] to [9], wherein the resin material further includes a resin powder containing a fluororesin having a melting point of 260 to 380 ° C.
[11] The melting point of the fluororesin contained in the resin powder having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group. The laminate of [10], which is an adhesive fluororesin at 260 to 380 ° C.
[12] The laminate according to any one of [1] to [11], wherein a fiber reinforced resin layer is bonded to the surface of the cured product layer opposite to the metal layer.
[13] A coating solution containing a fluoropolymer having a unit represented by the following formula U1.

(In the formula U1, X ¹ and X ² are each independently a hydrogen atom or a fluorine atom. Q ¹ is a single bond or an etheric oxygen atom. R ^f1 is a fluoroalkylene group, or It is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, Z ¹ is NR ¹ NR ² H, or NR ³ OR ^4. R ¹ , R ² , R ³ , R ⁴ is each independently a hydrogen atom or an alkyl group.)
[14] The coating liquid according to [13], further including at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin curing agent.
[15] The coating solution according to [13] or [14], further including a resin powder containing a fluororesin having a melting point of 260 to 380 ° C.
[16] The melting point of the fluororesin contained in the resin powder having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group The coating solution according to [15], which is an adhesive fluororesin having a temperature of 260 to 380 ° C.
[17] The coating solution of any one of [13] to [16] is applied to the surface of the metal layer to form a coating film, and the coating film is cured and cured by one or both of ultraviolet irradiation and heating. The manufacturing method of a laminated body which forms a physical layer.
[18] The method for producing a laminate according to [17], wherein a prepreg is joined to the surface of the cured product layer opposite to the metal layer by hot pressing.
[19] A method for manufacturing a printed circuit board, wherein a patterned circuit is formed by etching the metal layer of the laminate of any one of [1] to [12] to obtain a printed circuit board.

  According to the present invention, it has excellent electrical characteristics and can cope with high-frequency frequencies, the metal layer is difficult to oxidize during manufacturing, and the cured product layer and the metal layer, prepreg, etc. are adhered without using special high-temperature equipment. The laminated body excellent in property, its manufacturing method, the coating liquid used for manufacture of a laminated body, and the manufacturing method of a printed circuit board can be provided.

The following terms have the following meanings:
“Surface roughness Rz” means “maximum height Rz of surface roughness measured based on JIS C6515: 1998 (IEC61249-5-1: 1995)”.
The “melting point” means a temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
“Melt moldable” means exhibiting melt fluidity.
“Showing melt fluidity” means that there is a temperature at which the melt mass flow rate (MFR) is 0.01 to 1000 g / 10 min at a temperature higher by 20 ° C. or more than the melting point of the resin under a load of 49 N. Means.
The “unit” means a portion derived from a monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
A “monomer” is a compound having a polymerizable unsaturated bond such as a polymerizable double bond.
The “acid anhydride group” means a group represented by —C (═O) —O—C (═O) —.
The “carbonyl group-containing group” is a group containing a carbonyl group (—C (═O) —) in the structure.
“(Meth) acrylate” means acrylate or methacrylate.
“˜” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
A copolymer having units based on ethylene and units based on tetrafluoroethylene is referred to as an “ethylene / tetrafluoroethylene copolymer”. The same applies to other copolymers.
The unit represented by Formula U1 is referred to as unit U1. Units represented by other formulas are also shown in the same manner.

[Laminate]
The laminate of the present invention has a cured product layer made of a cured product of a resin material containing a curable fluororesin, and a surface roughness Rz on the surface in contact with the cured product layer provided on one side or both sides of the cured product layer. And a metal layer having a thickness of 5 μm or less.
In the laminate of the present invention, a fiber reinforced resin layer may be bonded to the surface of the cured product layer opposite to the metal layer.

  As a laminated structure of the laminated body of the present invention, a structure in which a metal layer and a cured product layer are laminated in this order (also referred to as “metal layer / cured product layer. Other laminated structures are also described in the same manner), metal layer / Examples of the cured layer / metal layer, metal layer / cured layer / fiber reinforced resin layer, and metal layer / cured layer / fiber reinforced resin layer / cured layer / metal layer.

(Cured product layer)
The cured product layer is a layer made of a cured product of a resin material containing a curable fluororesin. The curable fluororesin may be a fluororesin that is cured by light or a fluororesin that is cured by heat.

The curable fluororesin that is cured by light is preferably a curable fluororesin that is cured by irradiation with ultraviolet rays having a wavelength of 150 to 300 nm.
The curing temperature of the curable fluororesin that is cured by heat is preferably 23 ° C. or higher and lower than 380 ° C., more preferably 60 to 360 ° C., and even more preferably 100 to 340 ° C.

The curable fluororesin includes at least one curing site selected from the group consisting of a hydroxy group, a carboxy group, an acid amide group, an ester group, an unsaturated bond, an active hydrogen and a halogen (hereinafter also referred to as “curing site a”). )) (Hereinafter also referred to as “fluorinated polymer F1”), and a fluorine-containing polymer having unit U1 described later (hereinafter also referred to as “fluorinated polymer F2”). . The curable fluororesin preferably contains the fluorinated polymer F2 and more preferably consists only of the fluorinated polymer F2 from the viewpoint of better adhesion of the cured product layer to the metal layer, prepreg, and the like.
The curable fluororesin contained in the cured product layer may be one type or two or more types.

  Examples of the fluoropolymer F1 include polytetrafluoroethylene (PTFE) having a cured site a, ethylene / tetrafluoroethylene copolymer (ETFE) having a cured site a, and a fluoroolefin / vinyl ether copolymer having a cured site a. Can be illustrated.

Examples of the fluoroolefin include tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), trifluoroethylene (TrFE), vinylidene fluoride and the like, and TFE and CTFE are preferable.
As vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether, glycidyl vinyl ether, functional group having active hydrogen (hydroxyl group, carboxy group, amino group, etc.), hydrolyzable silyl group (alkoxysilyl group, etc.), epoxy group or oxetanyl group The vinyl ether having is preferable. As for carbon number of the alkyl group which vinyl ether has, 2-8 are preferable.

  The fluoropolymer F2 is a fluoropolymer having the following unit U1.

However, in the above formula U1, ^{X 1} and ^{X 2} are each independently a hydrogen atom or a fluorine atom. Q ¹ is a single bond or an etheric oxygen atom. R ^f1 is a fluoroalkylene group or a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms. Z ¹ is NR ¹ NR ² H or NR ³ OR ⁴ . R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group.

In the unit U1, Q ¹ is preferably an etheric oxygen atom.
When R ^f1 is a fluoroalkylene group, 1 to 6 carbon atoms are preferable, and 1 to 4 are particularly preferable. When the number of carbon atoms is 3 or more, a linear structure is preferable from the viewpoint of excellent thermal stability. The fluoroalkylene group is preferably a perfluoroalkylene group from the viewpoint of excellent thermal stability.
As the fluoroalkylene group for R ^f1, a perfluoroalkylene group having 1 to 6 carbon atoms is preferable, and a perfluoroalkylene group having 1 to 4 carbon atoms is particularly preferable.

When R ^f1 is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, the carbon number is preferably 2 to 10, and 2 to 6 is particularly preferable. When the number of carbon atoms is 3 or more, a linear structure is preferable from the viewpoint of excellent thermal stability. The fluoroalkylene group having an etheric oxygen atom is preferably a perfluoroalkylene group from the viewpoint of excellent thermal stability.
The fluoroalkylene group having an etheric oxygen atom of R ^f1 is preferably a C 2-10 perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms, and an etheric oxygen atom is interposed between carbon-carbon atoms. A perfluoroalkylene group having 2 to 6 carbon atoms is particularly preferred.

R ¹ , R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms from the viewpoint of high hydrogen bonding properties and excellent solubility of the fluoropolymer F2 in a liquid medium, A hydrogen atom, a methyl group or an ethyl group is more preferred, and a hydrogen atom is particularly preferred.

Examples of the unit U1 include the following units.
_{- [CF 2 -CF (O (} CF 2) 2 CONHNH 2)] -,
_{- [CF 2 -CF (O (} CF 2) 2 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 2 CONHOH)] -,
_{- [CF 2 -CF (O (} CF 2) 2 CONHOCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 3 CONHNH 2)] -,
_{- [CF 2 -CF (O (} CF 2) 3 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 3 CONHOH)] -,
_{- [CF 2 -CF (O (} CF 2) 3 CONHOCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 4 CONHNH 2)] -,
_{- [CF 2 -CF (O (} CF 2) 4 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 4 CONHOH)] -,
_{- [CF 2 -CF (O (} CF 2) 4 CONHOCH 3)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 2 CONHNH 2)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 2 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 2 CONHOH)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 2 CONHOCH 3)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 3 CONHNH 2)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 3 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 3 CONHOH)] -,
_{- [CF 2 -CF (OCF 2} CF (CF 3) O (CF 2) 3 CONHOCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 3 O (CF 2) 2 CONHNH 2)] -,
_{- [CF 2 -CF (O (} CF 2) 3 O (CF 2) 2 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 3 O (CF 2) 2 CONHOH)] -,
_{- [CF 2 -CF (O (} CF 2) 3 O (CF 2) 2 CONHOCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 2 O (CF 2) 2 CONHNH 2)] -,
_{- [CF 2 -CF (O (} CF 2) 2 O (CF 2) 2 CON (CH 3) NHCH 3)] -,
_{- [CF 2 -CF (O (} CF 2) 2 O (CF 2) 2 CONHOH)] -,
_{- [CF 2 -CF (O (} CF 2) 2 O (CF 2) 2 CONHOCH 3)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CONHNH 2)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CON (CH 3) NHCH 3)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CONHOH)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CONHOCH 3)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CF 2 OCF (CF 3) CONHNH 2)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CF 2 OCF (CF 3) CON (CH 3) NHCH 3)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CF 2 OCF (CF 3) CONHOH)] -,
_{- [CH 2 -CF (CF 2} OCF (CF 3) CF 2 OCF (CF 3) CONHOCH 3)] -.

The unit U1 is preferably a unit in which Z ¹ is NR ¹ NR ² H in terms of further excellent adhesion to a metal layer, a fiber reinforced resin layer, or the like. A unit in which Z ¹ is NR ³ OR ⁴ is preferable from the viewpoint of easy curing by ultraviolet irradiation. Among them, from the viewpoint of easy _{availability, - [CF 2 -CF (O} (CF 2) 3 CONHNH 2)] - or _{[CF 2 -CF (O (CF} 2) 3 CONHOH)] - are particularly preferred.
As the fluoropolymer F2, at least a part of the unit U1 is — [CF ₂ —CF (O (CF ₂ ) ₃ CONHNH ₂ )] — or [CF ₂ —CF (O (CF ₂ ) ₃ CONHOH)]. The fluorine-containing polymer which is-is preferable.
The unit U1 contained in the fluoropolymer F2 may be one type or two or more types.

The fluoropolymer F2 may have units other than the unit U1.
Examples of other units include units based on fluoroethylene (hereinafter also referred to as “FE units”).
Examples of the FE unit include units based on TFE (hereinafter also referred to as “TFE units”. Units based on other monomers are also described in the same manner), TrFE units, CTFE units, vinylidene fluoride units, and the like.

As the FE unit, a TFE unit, a TrFE unit, and a CTFE unit are preferable from the viewpoint of excellent light resistance. A TFE unit is more preferable in that the highly polar —COZ ¹ group is likely to be present at the interface, thereby further improving the adhesion of the cured layer to the prepreg and the like, and excellent wettability of the fluoropolymer F2. Compared with the fluoropolymer F2 having a TFE unit, the crystallinity is low, light scattering is less likely to occur, and the transparency is high, so the TrFE unit and the CTFE unit are more preferable. From the viewpoint of excellent solubility in a liquid medium, TrFE units are more preferable.
The unit U2 contained in the fluoropolymer F2 may be one type or two or more types.

The fluoropolymer F2 may have the following unit U2 (excluding the FE unit).
^{- [CX 3 X 4 -CY 1} Y 2] - ··· formula U2
However, in the formula U2, ^{X 3} and ^{X 4} are each independently a hydrogen atom, a fluorine atom or a chlorine atom. Y ¹ is a hydrogen atom, a fluorine atom or a chlorine atom. Y ² represents a hydrogen atom, a fluoroalkyl group, a fluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, a fluoroalkoxy group, or a carbon having an etheric oxygen atom between carbon-carbon atoms. A fluoroalkoxy group having a number of 2 or more.

The number of carbon atoms of the fluoroalkyl group Y ² is preferably 1 to 15, 1 to 6 is particularly preferred. The fluoroalkyl group for Y ² is preferably a perfluoroalkylene group, more preferably a C 1-6 perfluoroalkyl group, and particularly preferably —CF ₃ from the viewpoint of excellent thermal stability.
Carbon of Y ² - the number of carbon atoms having 2 or more fluoroalkyl group having an etheric oxygen atom between carbon atoms, preferably 2 to 15, 2 to 6 is particularly preferred. The fluoroalkylene group having an etheric oxygen atom of Y ² is preferably a perfluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms from the viewpoint of excellent thermal stability. A C 2-6 perfluoroalkyl group having an etheric oxygen atom in between is particularly preferred.

The number of carbon atoms in the fluoroalkoxy group Y ² is preferably 1 to 15, 1 to 6 is particularly preferred. As the fluoroalkoxy group for Y ^2, a perfluoroalkoxy group having 1 to 6 carbon atoms is preferable from the viewpoint of excellent thermal stability, and —OCF ₃ , —OCF ₂ CF ₃ , —O (CF ₂ ) ₂ CF ₃ , — O (CF ₂ ) ₃ CF ₃ is particularly preferred.
Y ² carbon - carbon atoms having 2 or more fluoroalkoxy group having an etheric oxygen atom between carbon atoms, preferably 2 to 15, 2 to 6 is particularly preferred. The fluoroalkoxy group having an etheric oxygen atom of Y ² is preferably a perfluoroalkoxy group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms from the viewpoint of excellent thermal stability. A C 2-6 perfluoroalkoxy group having an etheric oxygen atom in between is particularly preferred.

The number of carbon atoms of the fluoroalkenyl group Y ² is the cyclization reaction does not proceed in the molecule, from the viewpoint of easy synthesis, 5-15 are preferred. The fluoroalkenyl group of Y ² is preferably a perfluoroalkenyl group from the viewpoint of excellent thermal stability, and — (CF ₂ ) ₄ CF═CF ₂ , — (CF ₂ ) ₅ CF═CF ₂ and (CF ₂ ) ₆ CF = CF ₂ is particularly preferred.
Y ² carbon - carbon atoms having 2 or more fluoro alkenyl group having an etheric oxygen atom between carbon atoms, preferably 2 to 15, 2 to 6 is particularly preferred. The fluoroalkenyl group having an etheric oxygen atom of Y ² is preferably a perfluoroalkenyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms from the viewpoint of excellent thermal stability. A C 2-6 perfluoroalkenyl group having an etheric oxygen atom therebetween is particularly preferred.

Examples of the unit U2 include the following units.
_{- [CH 2 -CH 2] -} , - [CF 2 -CF (CF 3)] -, - [CH 2 -CF (CF 3)] -, - [CF 2 -CF (OCF 3)] -, - _{[CF 2 -CF (OCF 2 CF} 3)] -, - [CF 2 -CF (O (CF 2) 2 CF 3)] -, - [CF 2 -CF (O (CF 2) 3 CF 3)] _{-, - [CF 2 -CF (} OCF 2 CF (CF 3) O (CF 2) 2 CF 3)] -, - [CF 2 -CF ((CF 2) 4 CF = CF 2)] -, - [ _{CF 2 -CF ((CF 2)} 5 CF = CF 2)] -, - [CF 2 -CF ((CF 2) 6 CF = CF 2)] - or the like.

As the unit U2, from the point that the glass transition temperature of the fluoropolymer F2 is lowered, the fluidity is excellent, the moldability is excellent, and the fluoropolymer F2 is easily cured by heating or ultraviolet irradiation. _{- [CH 2 -CH 2] -} , - [CF 2 -CF (CF 3)] -, - [CF 2 -CF (OCF 3)] -, - [CF 2 -CF (O (CF 2) 2 CF _3)] - or _{[CF 2 -CF (OCF 2 CF} (CF 3) O (CF 2) 2 CF 3)] - is preferably.
The unit U2 contained in the fluoropolymer F2 may be one type or two or more types.

The unit U2 can be formed by polymerizing a monomer represented by the following formula m2.
CX ³ X ⁴ = CY ¹ Y ² ... Formula m2
However, X < ³ >, X < ⁴ >, Y < ¹ >, Y < ² > in Formula m2 is the same as Formula U2.

  The fluoropolymer F2 may have the following unit U3.

In Formula U3, X ⁵ , X ⁶ and X ⁷ are each independently a fluorine atom or a hydrogen atom, two Q ² are each independently a single bond or an etheric oxygen atom, and R ^f2 has 1 carbon atom. Or a fluoroalkylene group having 2 to 25 carbon atoms having an etheric oxygen atom between carbon-carbon atoms. Two X ⁵ in the unit U3 may be the same or different. The same applies to the two X ⁶ and the two X ⁷ . The two Q ² 'in the unit U3 may be the same or different.

In the unit U3, X ⁵ , X ⁶ and X ⁷ are all preferably fluorine atoms or hydrogen atoms. When X ⁵ , X ⁶ , and X ⁷ are all fluorine atoms, the two Q ² are preferably etheric oxygen atoms. When all of X ⁵ , X ⁶ and X ⁷ are hydrogen atoms, the two Q ² are preferably single bonds.

The number of carbon atoms of the fluoroalkylene group R ^f2 is 1-6, 2-6 are preferred. In the case where R ^f2 is a fluoroalkylene group having 3 to 6 carbon atoms, a linear structure is preferable from the viewpoint of excellent thermal stability. The fluoroalkylene group for R ^f2 is preferably a perfluoroalkylene group from the viewpoint of excellent thermal stability. The fluoroalkylene group R ^f2, preferably perfluoroalkylene group having 1 to 6 carbon atoms, and more preferably perfluoroalkylene group having 2 to 6 carbon atoms.

The carbon number of the fluoroalkylene group having an etheric oxygen atom between the carbon atoms of R ^f2 is 2 to 25, preferably 2 to 10, and particularly preferably 2 to 6. When the fluoroalkylene group having an etheric oxygen atom has 3 or more carbon atoms, a linear structure is preferred from the viewpoint of excellent thermal stability. The fluoroalkylene group having an etheric oxygen atom is preferably a perfluoroalkylene group from the viewpoint of excellent thermal stability.
The fluoroalkylene group having an etheric oxygen atom of R ^f2 is preferably a C 2-10 perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms, and an etheric oxygen atom between the carbon-carbon atoms. The perfluoroalkylene group having 2 to 6 carbon atoms is more preferable,-(CF ₂ O)-,-(CF ₂ CF ₂ O)-,-(CF ₂ CF (CF ₃ ) O)-, (CF ₂ CF ₂ CF ₂ O) - it is more preferred.

As the unit U3, X ⁵ , X ⁶ , and X ⁷ are all fluorine atoms, two Q ² are both etheric oxygen atoms, and R ^f2 is — (CF ₂ ) ₂ —, — (CF ₂ ) ₃ −, — (CF ₂ ) ₄ —, — (CF ₂ ) ₆ —, — (CF ₂ ) ₄ OCF (CF ₃ ) CF ₂ —, — (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ —, _{- (CF 2 CF 2 O)} 2 -, - a a a unit _{- CF 2 O (CF 2 CF} 2 O) 2 - or _{CF 2 CF (CF 3) O} (CF 2) 2 OCF (CF 3) CF 2 It can be illustrated. X ⁵ , X ⁶ and X ⁷ are all hydrogen atoms, two Q ² are both single bonds, and R ^f2 is — (CF ₂ ) ₂ —, — (CF ₂ ) ₄ — or ( An example of the unit is CF ₂ ) ₆ —.

  As the unit U3, the following units U31 and U32 are particularly preferable from the viewpoint of easy availability.

The unit U3 can be formed by polymerizing a monomer represented by the following formula m3 (hereinafter also referred to as “monomer m3”).
X ⁵ X ⁶ C = CX ⁷ −Q ² −R ^f2 −Q ² −CX ⁷ = CX ⁵ X ⁶ ... M3
In formula m3, X ⁵ , X ⁶ , X ⁷ , Q ² , and R ^f2 are the same as in formula U3.

Examples of the monomer m3 include the following monomers.
_{CF 2 = CFO (CF 2)} 2 OCF = CF 2,
_{CF 2 = CFO (CF 2)} 3 OCF = CF 2,
_{CF 2 = CFO (CF 2)} 4 OCF = CF 2,
_{CF 2 = CFO (CF 2)} 6 OCF = CF 2,
_{CF 2 = CFO (CF 2)} 4 OCF (CF 3) CF 2 OCF = CF 2,
_{CF 2 = CFO (CF 2)} 2 OCF (CF 3) CF 2 OCF = CF 2,
_{CF 2 = CFO (CF 2 CF} 2 O) 2 OCF = CF 2,
_{CF 2 = CFOCF 2 O (CF} 2 CF 2 O) 2 OCF = CF 2,
_{CF 2 = CFOCF 2 CF (CF} 3) O (CF 2) 2 OCF (CF 3) CF 2 OCF = CF 2,
_{CH 2 = CH- (CF 2)} 2 -CH = CH 2,
_{CH 2 = CH- (CF 2)} 4 -CH = CH 2,
_{CH 2 = CH- (CF 2)} 6 -CH = CH 2.

  The fluoropolymer F2 may have units U4 other than the units U1 to U3 and the FE unit.

As the fluorine-containing polymer F2, a fluorine-containing polymer having units U1, FE units and units U2, and a fluorine-containing polymer having units U1, FE units, units U2 and units U3 are preferable. When the fluoropolymer F2 has the unit U3, Z ¹ of the unit U1 is particularly preferably NR ¹ NR ² H.

The content of the group represented by —COZ ¹ in the fluoropolymer F2 is preferably 0.01 to 4.0 mmol / g, and preferably 0.05 to 2.0 mmol with respect to the mass of the fluoropolymer F2. / G is more preferable, and 0.1 to 1.0 mmol / g is more preferable. When the content is at least the lower limit of the above range, the adhesion of the cured product layer to the prepreg and the like is further improved, and the solubility in the liquid medium is further improved. When the content is less than or equal to the upper limit of the above range, when the coating film containing the fluoropolymer F2 is cured by ultraviolet irradiation, it can be easily cured uniformly in the thickness direction, and foaming during curing can be suppressed.

The content of the group represented by —COZ ^{1 in} which Z ¹ in the fluoropolymer F2 is NR ¹ NR ² H is 0.01 to 4.0 mmol / g with respect to the mass of the fluoropolymer F2. Is preferable, 0.05 to 2.0 mmol / g is more preferable, and 0.1 to 1.0 mmol / g is more preferable.
The content of the group represented by —COZ ^{1 in} which Z ¹ in the fluoropolymer F2 is NR ³ OR ⁴ is 0.01 to 4.0 mmol / g with respect to the mass of the fluoropolymer F2. Preferably, 0.05 to 2.0 mmol / g is more preferable, and 0.1 to 1.0 mmol / g is more preferable.
The content of the group represented by -COZ ¹ in the fluoropolymer F2 can be calculated by ¹⁹ F-NMR measurement.

  The ratio of the unit U1 in the fluoropolymer F2 is preferably 0.1 to 10.0 mol%, more preferably 0.3 to 8.0 mol%, and more preferably 0.5 to 5. 0 mol% is more preferable, and 1.0 to 3.0 mol% is particularly preferable. If the ratio of the unit U1 is not less than the lower limit of the above range, the adhesion of the cured product layer to the prepreg and the like is further improved, and the solubility in the liquid medium is further improved. When the ratio of the unit U1 is not more than the upper limit of the above range, the coating film containing the fluoropolymer F2 can be easily cured uniformly in the thickness direction when cured by ultraviolet irradiation, and foaming during curing can be suppressed.

  The proportion of the FE units in the fluoropolymer F2 is preferably 10 to 90 mol%, more preferably 30 to 80 mol%, still more preferably 50 to 80 mol%, and 60 to 80 mol% with respect to all units. Is particularly preferred. When the ratio of the FE unit is equal to or greater than the lower limit of the above range, the mechanical strength of the cured product is improved. If the ratio of the FE unit is not more than the upper limit of the above range, the solubility in the liquid medium is high, and a uniform coating film tends to be formed.

  The proportion of the unit U2 in the fluoropolymer F2 is preferably 10 to 50 mol%, more preferably 15 to 50 mol%, still more preferably 20 to 40 mol%, and more preferably 25 to 35 mol%, based on all units. Is particularly preferred. If the ratio of the unit U2 is not less than the lower limit of the above range, light scattering due to crystallinity is suppressed, and curing by ultraviolet irradiation is likely to proceed. If the ratio of the unit U2 is not more than the upper limit of the above range, a polymer having excellent mechanical strength tends to be obtained.

The proportion of the unit U3 in the fluoropolymer F2 is preferably from 0.001 to 5.0 mol%, more preferably from 0.01 to 3.0 mol%, more preferably from 0.1 to 1. 0 mol% is more preferable, and 0.3 to 0.7 mol% is particularly preferable. If the ratio of unit U3 is more than the lower limit of the said range, the elasticity of hardened | cured material will go up and adhesive strength with a base material will improve. If the ratio of the unit U3 is not more than the upper limit of the above range, the fluidity at the time of molding tends to be high and a uniform coating film tends to be obtained.
The ratio of each unit in the fluoropolymer F2 can be calculated by ¹⁹ F-NMR and ¹ H-NMR measurements.

The mass average molecular weight of the fluorinated polymer F2 is preferably from 2,000 to 200,000, more preferably from 20,000 to 100,000. If the mass average molecular weight is at least the lower limit of the above range, the cured product tends to be excellent in mechanical strength and heat resistance. If a mass average molecular weight is below the upper limit of the said range, the fluidity | liquidity at the time of shaping | molding will be high, and there exists a tendency for a uniform coating film to be obtained easily.
A mass average molecular weight is calculated | required as a PMMA (polymethylmethacrylate) conversion molecular weight by gel permeation chromatography (GPC).

  The glass transition temperature of the fluoropolymer F2 (hereinafter also referred to as “Tg”) is preferably −40 ° C. or higher, more preferably −20 to 180 ° C., and still more preferably 0 to 150 ° C. If Tg of fluoropolymer F2 is more than the said lower limit, the adhesiveness of a hardened | cured material layer and a metal layer will further improve.

The production method of the fluoropolymer F1 and the fluoropolymer F2 is not particularly limited, and a monomer for forming each unit is used, and a known polymerization method (for example, as described in International Publication No. 2015/0987773). Method).
The unit U1 in the fluoropolymer F2 is obtained from the hydrazine compound represented by the following formula 1 and the hydroxylamine compound represented by the following formula 2 after obtaining the fluoropolymer having the following unit U′1. It can be formed by reacting either one or both.

HR ¹ N—NR ² H Formula 1
NHR ³ OR ⁴ ... Formula 2
However, ^{R 5} in the formula m1 is an alkyl group. X ¹ , X ² , R ^f1 , R ¹ , R ² , R ³ , R ⁴ in Formula m1, Formula 1 and Formula 2 are the same as in Formula U1.

Examples of the hydrazine compound represented by Formula 5 include hydrazine, hydrazine monohydrate, methyl hydrazine, and 1,2-dimethylhydrazine.
Examples of the hydroxylamine compound represented by Formula 6 include hydroxylamine, N-methylhydroxylamine, N, O-dimethylhydroxylamine, and isopropylhydroxylamine.

One or more compounds selected from the group consisting of a hydrazine compound and a hydroxylamine compound are a hydrazine compound and a hydroxylamine reacted with 1 mol of a group represented by —COOR ⁵ of a fluoropolymer having a unit U′1. 1.0-20.0 mol is preferable, as for the ratio of a compound, 1.2-10.0 mol is more preferable, and 1.5-5.0 mol is especially preferable.
The reaction can be performed in the presence of various solvents such as a fluorine-containing solvent, an ether solvent, and an ester solvent.

The resin material forming the cured layer is at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent and an amino resin curing agent (hereinafter also referred to as “curing agent A”). .) May be included.
Curing agent A reacts with the group represented by -COZ ¹ of fluoropolymer F2 to form a crosslinked structure. Therefore, when using the fluoropolymer F2 as a curable fluororesin, sclerosis | hardenability improves by using the hardening | curing agent A together. Curing by the reaction between the curing agent A and the fluoropolymer F2 proceeds at a temperature of about 23 to 150 ° C. The curing agent A contained in the resin material may be one type or two or more types.

Examples of the isocyanate curing agent include non-yellowing isocyanate, non-yellowing isocyanate-modified product, aromatic isocyanate, and aromatic isocyanate-modified product. The isocyanate group of the isocyanate curing agent is not blocked.
Non-yellowing isocyanates include alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI); cyclohexyl isocyanate and n-hexyl isocyanate and the like. A monoisocyanate can be illustrated.

  The non-yellowing isocyanate-modified product is represented by -C (= O) -NH-, which is an isocyanurate of an aliphatic diisocyanate or an alicyclic diisocyanate, an aliphatic diisocyanate or an alicyclic diisocyanate modified with a polyol or polyamine. A modified product having a structure represented by -C (= O) -NH-, wherein a part of the isocyanate group of an isocyanurate of an aliphatic diisocyanate or an alicyclic diisocyanate is modified with a polyol. It can be illustrated.

Examples of the aromatic isocyanate include methylene diphenyl 4,4′-diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, and phenyl isocyanate.
Examples of the modified aromatic isocyanate include an isocyanurate of an aromatic diisocyanate, a modified of an aromatic diisocyanate modified with a polyol or a polyamine, a structure represented by -C (= O) -NH-, and an aromatic diisocyanate. A modified product having a structure represented by -C (= O) -NH-, in which a part of the isocyanate group of the isocyanurate product is modified with a polyol, can be exemplified.

The blocked isocyanate curing agent is obtained by blocking the isocyanate group of the isocyanate curing agent.
Isocyanate groups can be blocked with epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), pyralidine, triazine (TA), ammonia, methanol, bicarbonate, etc. .

Examples of amino resin curing agents include melamine resins, guanamine resins, sulfoamide resins, urea resins, and aniline resins. Especially, a melamine resin is preferable at the point that a cure rate is quick.
Specific examples of the melamine resin include alkyl etherified melamine resins that are alkyl etherified. Especially, the melamine resin substituted by any one or both of the methoxy group and the butoxy group is preferable.

  When the resin material contains the curing agent A, the content of the curing agent A in the resin material is preferably 0.1 to 100 parts by mass, and 0.5 to 60 parts by mass with respect to 100 parts by mass of the curable fluororesin. Part is more preferable, and 1 to 10 parts by mass is further preferable. If content of the hardening | curing agent A is more than the lower limit of the said range, a tougher hardened | cured material layer will be easy to be formed. If content of the hardening | curing agent A is below the upper limit of the said range, it will be easy to suppress that foaming arises in a hardened | cured material layer.

  The resin material forming the cured product layer further includes a resin powder (hereinafter also referred to as “resin powder B”) containing a fluororesin having a melting point of 260 to 380 ° C. (hereinafter also referred to as “fluororesin F3”). But you can. The fluororesin F3 contained in the resin powder B may be one type or two or more types.

The fluororesin F3 is preferably melt-moldable. The melting point of the melt-moldable fluororesin F3 is preferably 260 to 320 ° C, more preferably 280 to 320 ° C, further preferably 295 to 315 ° C, and particularly preferably 295 to 310 ° C.
In addition, melting | fusing point of the fluororesin F3 can be adjusted with the kind of unit, content rate, molecular weight, etc. which comprise the fluororesin F3. For example, the melting point tends to increase as the proportion of the unit u1 described later increases.

As the fluororesin F3, PTFE, polychlorotrifluoroethylene (PCTFE), ETFE, ethylene / CTFE copolymer (ECTFE), CTFE / TFE copolymer, and TFE / hexafluoropropylene (hereinafter referred to as “HFP”) are also described. ) Copolymer (FEP), TFE / perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”) copolymer (PFA), polyvinylidene fluoride (PVdF), and the like.
The fluororesin F3 is preferably at least one selected from the group consisting of PTFE, PCTFE, ETFE, ECTFE, CTFE-TFE copolymer, FEP, PFA and PVdF, and has electrical characteristics (dielectric constant, dielectric loss tangent) and heat resistance. From the viewpoint of properties, PFA and FEP are more preferable, and PFA is more preferable.

  As the fluororesin F3, an adhesive having a melting point of 260 to 320 ° C. having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group A fluororesin (hereinafter also referred to as “adhesive fluororesin F31”) is preferable. The fluororesin F3 may be a fluororesin having a melting point of 260 to 320 ° C. that does not have an adhesive functional group.

The adhesive functional group that the adhesive fluororesin F31 has may be one type or two or more types. The adhesive functional group is preferably a carbonyl group-containing group from the viewpoint of adhesion at the interface between the cured product layer and the prepreg.
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, an acid anhydride group, and the like.

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. In addition, carbon number of this 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. That is, the haloformyl group is preferably a fluoroformyl group (also referred to as a carbonyl fluoride group).
The alkoxy group in the alkoxycarbonyl group may be linear or branched, preferably an alkoxy group having 1 to 8 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

The content of the adhesive functional group in the adhesive fluororesin F31 is preferably 10 to 60000, more preferably 100 to 50000, with respect to 1 × 10 ⁶ main chain carbon atoms of the adhesive fluororesin F31. 10,000 is more preferable, and 300-5000 is particularly preferable. If the content of the adhesive functional group is at least the lower limit of the above range, the adhesion at the interface between the cured product layer and an object to be bonded such as a prepreg is further improved. When the content of the adhesive functional group is not more than the upper limit of the above range, the heat resistance and color of the adhesive fluororesin F31 are good.

  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 ratio of units having an adhesive functional group in all units constituting the adhesive fluororesin F31 (mol%) ) And the content of the adhesive functional group can be calculated from the ratio.

  Examples of the adhesive fluororesin F31 include a fluorine-containing polymer having a unit having an adhesive functional group and a terminal group having an adhesive functional group. Specific examples include PFA having an adhesive functional group, FEP having an adhesive functional group, ETFE having an adhesive functional group, and the like.

  As the adhesive fluororesin F31, a cyclic hydrocarbon monomer having an acid anhydride group and a unit u1 based on TFE or CTFE from the viewpoint of excellent adhesion to a prepreg and the like and more excellent electrical characteristics. , Also referred to as “an acid anhydride monomer”) and a fluorine-containing polymer having a unit u3 based on a fluorine-containing monomer (excluding TFE and CTFE) (hereinafter, “ It is also referred to as “fluorinated polymer X”.).

  The monomer constituting the unit u1 is preferably TFE from the viewpoint of excellent heat resistance.

  Examples of the acid anhydride monomer include itaconic anhydride (hereinafter also referred to as “IAH”), citraconic anhydride (hereinafter also referred to as “CAH”), and 5-norbornene-2,3-dicarboxylic acid anhydride. (Hereinafter also referred to as “NAH”), maleic anhydride and the like. As the acid anhydride monomer, IAH, CAH and NAH are preferable, and IAH and NAH are more preferable. One type of acid anhydride monomer may be used alone, or two or more types may be used in combination.

  In the fluorine-containing polymer X, 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.) may be included. When a unit based on the dicarboxylic acid is included, the content of the 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. For example, fluoroolefins excluding TFE (vinyl fluoride, vinylidene fluoride, TFE, HFP). , Hexafluoroisobutylene, etc.), PAVE, CH ₂ = CX ⁸ (CF ₂ ) _q X ⁹ (where X ⁸ is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, and X ⁹ is hydrogen. An atom or a fluorine atom) (hereinafter also referred to as “FAE”), and the like.

As the fluorine-containing monomer constituting the unit u3, at least one selected from the group consisting of HFP, PAVE and FAE is preferable, and PAVE is particularly preferable.
As PAVE, CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F and the like, and PPVE is preferable.

The _{FAE, 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 preferable, and CH ₂ ═CH (CF ₂ ) ₄ F (hereinafter also referred to as “PFBE”) and CH ₂ ═CH (CF ₂ ) ₂ F (hereinafter referred to as “PFEE”). Are preferred).

The preferable ratio of each unit to the total amount of the unit u1, the unit u2 and the unit u3 in the fluoropolymer X is as follows.
The proportion of the unit u1 is preferably 90 to 99.89 mol%, more preferably 95 to 99.47 mol%, and still more preferably 96 to 98.95 mol%.
The proportion of the unit u2 is preferably 0.01 to 3.0 mol%, more preferably 0.03 to 2.0 mol%, and even more preferably 0.05 to 1.0 mol%.
The proportion of the unit u3 is preferably 0.1 to 9.99 mol%, more preferably 0.5 to 9.97 mol%, and further preferably 1.0 to 9.95 mol%.
The ratio of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluoropolymer X.

In addition to the units u1 to u3, the fluorinated polymer X may have a unit u4 based on a non-fluorinated monomer (however, excluding an acid anhydride monomer).
As the non-fluorine monomer, a non-fluorine compound having one polymerizable carbon-carbon double bond is preferable, and examples thereof include olefins (ethylene, propylene, 1-butene, etc.), vinyl esters (vinyl acetate, etc.), and the like. Can be mentioned. A non-fluorine-type monomer may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the fluoropolymer X include TFE / NAH / PPVE copolymer, TFE / IAH / PPVE copolymer, TFE / CAH / PPVE copolymer, TFE / IAH / HFP copolymer, TFE / CAH. / HFP copolymer, TFE / IAH / PFBE / ethylene copolymer, TFE / CAH / PFBE / ethylene copolymer, TFE / IAH / PFEE / ethylene copolymer, TFE / CAH / PFEE / ethylene copolymer, Examples thereof include TFE / IAH / HFP / PFBE / ethylene copolymer.
As the fluoropolymer X, PFA having an adhesive functional group is preferable, and a TFE / NAH / PPVE copolymer, a TFE / IAH / PPVE copolymer, and a TFE / CAH / PPVE copolymer are more preferable.

A fluoropolymer having an adhesive functional group such as fluoropolymer X can be produced by a conventional method.
As the adhesive fluororesin F31, a fluoropolymer having an adhesive functional group as a main chain terminal group may be used. The fluorine-containing polymer having an adhesive functional group as a main chain terminal group is a chain transfer agent (acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol, etc.) that provides an adhesive functional group when the monomer is polymerized. ) Or a polymerization initiator (di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, etc.).

The resin powder B may include a resin other than the fluororesin F3.
The ratio of the fluororesin F3 in the resin powder B is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass with respect to the total amount of the resin powder B. .

  The average particle size of the resin powder B is preferably 0.3 to 6.0 μm, more preferably 0.4 to 5.0 μm, further preferably 0.5 to 4.5 μm, and particularly preferably 0.7 to 4.0 μm. Preferably, 1 to 3.5 μm is most preferable. If the average particle diameter of the resin powder B is not less than the lower limit of the above range, the resin powder B is easy to handle. If the average particle diameter of the resin powder B is not more than the upper limit of the above range, the dispersibility of the resin powder B is excellent.

The average particle diameter of the resin powder is a volume-based cumulative 50% diameter (D50) determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of particles being 100%, and the particle diameter is the point at which the cumulative volume is 50% on the cumulative curve.
The average particle diameter of the resin powder B can be adjusted by pulverization, classification (sieving, etc.) and the like.

  When the resin material forming the cured product layer contains the resin powder B, the content of the resin powder B in the resin material is preferably 0.1 to 80 parts by mass with respect to 100 parts by mass of the curable fluororesin. -60 mass parts is more preferable. If the content of the resin powder B is equal to or higher than the lower limit of the above range, the electrical properties of the cured product layer are more excellent, and excellent transmission efficiency can be obtained when the cured product layer is used for a printed circuit board. . If content of resin powder B is below the upper limit of the said range, detachment | desorption of the powder from a hardened | cured material layer can be suppressed.

The resin material forming the cured product layer may contain other components other than the curable fluororesin, the curing agent A, and the resin powder B as long as the effects of the present invention are not impaired.
Examples of other components include fluorinated resins other than the curable fluororesin and fluororesin F3, non-fluorinated resins not containing fluorine atoms (polyester, polyolefin, etc.), fillers (silica, clay, talc, etc.) and the like.
1 type may be sufficient as the other component contained in the resin material, and 2 or more types may be sufficient as it.

  1-500 micrometers is preferable and, as for the thickness of a hardened | cured material layer, 3-300 micrometers is more preferable. If the thickness of the cured product layer is equal to or greater than the lower limit of the above range, a coating film can be formed without appearance defects of pinholes and repellency. If the thickness of a hardened | cured material layer is below the upper limit of the said range, the curvature of a hardened | cured material layer can be suppressed.

The water vapor transmission coefficient of the cured product layer is preferably 20 g · mm / m ² · day or less, and more preferably 10 g · mm / m ² · day or less. If the water vapor transmission coefficient of the cured product layer is less than or equal to the above upper limit value, the etching solution is less likely to penetrate into the cured product layer during etching of the metal layer in the production of a printed circuit board, and a fine circuit can be easily formed without etching defects. The water vapor transmission coefficient of the cured product layer is preferably as low as possible.
In addition, the water vapor transmission coefficient of a hardened | cured material layer is measured by the method based on JISZ0208.

(Metal layer)
Examples of the metal constituting the metal layer include iron, stainless steel, aluminum, copper, brass, nickel, zinc, titanium, and alloys of these metals. For printed circuit board applications, copper or copper alloy, stainless steel, nickel or nickel alloy (including 42 alloy), aluminum or aluminum alloy are preferable, and copper is particularly preferable.
As the metal layer, a layer made of copper foil such as rolled copper foil or electrolytic copper foil is particularly preferable.

The surface roughness Rz of the surface of the metal layer in contact with the cured product layer is 4.5 μm or less, preferably 0.05 to 3 μm. When the surface roughness Rz of the metal layer is equal to or less than the upper limit value, a printed circuit board that has excellent electrical characteristics and can cope with a frequency in a high frequency band can be manufactured.
The thickness of the metal layer is not particularly limited, and a thickness that can exhibit a sufficient function may be selected depending on the application.

  The peel strength at the interface between the cured product layer and the metal layer of the laminate is preferably 5 N / 10 mm or more, more preferably 7 N / 10 mm or more, and further preferably 8 N / 10 mm or more.

(Fiber reinforced resin layer)
The fiber reinforced resin layer is a layer containing a reinforced fiber base material and a matrix resin.
Examples of reinforcing fibers used for the reinforcing fiber base include inorganic fibers, metal fibers, and organic fibers. Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber. Examples of the metal fiber include aluminum fiber, brass fiber, and stainless steel fiber. Examples of the organic fiber include aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber, and the like.
For printed circuit board applications, glass fibers are preferred as reinforcing fibers. The reinforcing fiber may be surface-treated. Reinforcing fibers may be used alone or in combination of two or more.

The embodiment of the reinforcing fiber base is not particularly limited, and a reinforcing fiber bundle composed of a plurality of reinforcing fibers, a cloth formed by weaving the reinforcing fiber bundle, and a unidirectional reinforcement in which a plurality of reinforcing fibers are aligned in one direction. Examples thereof include a fiber bundle, a unidirectional cloth composed of the unidirectional reinforcing fiber bundle, a combination thereof, and a stack of a plurality of reinforcing fiber bundles.
As the reinforcing fiber, a continuous long fiber having a length of 10 mm or more is preferable. The reinforcing fibers do not need to be continuous over the entire length in the length direction or the entire width in the width direction of the reinforcing fiber base material, and may be divided in the middle.

The matrix resin may be a thermoplastic resin or a cured product of a thermosetting resin. The present invention is particularly effective when a thermoplastic resin having a melting point of 280 ° C. or less or a cured product of a thermosetting resin having a thermosetting temperature of 280 ° C. or less is used as the matrix resin.
A matrix resin may be used individually by 1 type, and may use 2 or more types together.

As the matrix resin, a cured product of a thermosetting resin is preferable.
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 Examples thereof include ester resins, urea resins, diallyl phthalate resins, melanin resins, guanamine resins, melamine-urea cocondensation resins, and fluororesins having reactive groups (excluding the adhesive fluororesin F31). Especially, from a point useful for a printed circuit board use, as a thermosetting resin, at least 1 sort (s) chosen from the group which consists of an epoxy resin, polyphenylene oxide, polyphenylene ether, and polybutadiene is preferable. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

  As thermoplastic resins, polyester resins (polyethylene terephthalate, etc.), polyolefin resins (polyethylene, etc.), styrene resins (polystyrene, etc.), polycarbonate, polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, polyallylsulfone ( Polyethersulfone, etc.), aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, polyphenylene ether, PTFE, TFE / PAVE copolymer, TFE / HFP copolymer, Examples thereof include a fluororesin such as PCTFE.

  The thickness of the fiber reinforced resin layer can be appropriately set, is preferably 10 μm or more and 5 mm or less, more preferably 30 μm or more and 3 mm or less, and particularly preferably 80 μm or more and 1 mm or less.

  The peel strength at the interface between the cured product layer and the fiber reinforced resin layer in the laminate is preferably 5 N / 10 mm or more, more preferably 7 N / 10 mm or more, and even more preferably 8 N / 10 mm or more.

[Manufacturing method of laminate]
As a method for producing the laminate of the present invention, a coating liquid containing a curable fluororesin is applied to the surface of a metal layer to form a coating film, and the coating film is cured by one or both of ultraviolet irradiation and heating. And a method of forming a cured product layer.

(Coating solution)
In the present invention, a coating solution containing a fluorinated polymer F2 as a curable fluororesin is used from the viewpoint that adhesion between the cured product layer and the metal layer and adhesion between the cured product layer and another substrate such as a prepreg are more excellent. Is particularly effective.
In the coating solution, a curing agent A, powder B, and other components are blended as necessary.

  The liquid medium used for the coating solution is not particularly limited, and water; alcohols such as methanol and ethanol; nitrogen-containing compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfur-containing compounds such as dimethyl sulfoxide; ethers such as diethyl ether and dioxane; esters such as ethyl lactate and ethyl acetate; ketones such as methyl ethyl ketone and methyl isopropyl ketone; glycol ethers such as ethylene glycol monoisopropyl ether; methyl cellosolve And cellosolves such as ethyl cellosolve. As a liquid medium, 1 type may be used independently and 2 or more types may be used together.

  1-40 mass% is preferable and, as for the solid content concentration of a coating liquid, 5-20 mass% is more preferable.

The application method of the coating solution is not particularly limited, and is a spray method, roll coating method, spin coating method, bar coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating. Examples thereof include a die coating method, a fountain Mayer bar method, and a slot die coating method.
After application of the coating solution, the coating film may be dried as necessary.

When the coating film is cured by ultraviolet irradiation, the wavelength of the ultraviolet light is preferably 150 to 300 nm. Examples of the light source that irradiates ultraviolet rays having a wavelength of 150 to 300 nm include low pressure mercury lamps, metal halide lamps, excimer lasers, flash lamps, deep ultraviolet (Deep UV), vacuum ultraviolet (VUV), and deep ultraviolet LEDs.
The irradiation time of ultraviolet rays can be appropriately set and is preferably 1 to 30 minutes.

When the coating film is cured by heating, the heating method is not particularly limited, and examples thereof include oven heating, heat ray irradiation heating, heating by a continuous drying furnace, heating by a hot plate or a hot roll.
The heating temperature of the coating film is preferably 23 to 380 ° C, more preferably 100 to 340 ° C.
The heating time can be appropriately set and is preferably 1 to 30 minutes.

  When the fiber reinforced resin layer is joined to the surface of the cured product layer opposite to the metal layer, the joining method includes a method of joining the prepreg to the surface of the cured product layer opposite to the metal layer by hot pressing. .

In this invention, you may surface-treat the surface of the side joined to the prepreg of a hardened | cured material layer. As the surface treatment, plasma treatment is preferable.
The plasma irradiation apparatus used for the plasma processing is not particularly limited, and is a high frequency induction method, capacitively coupled electrode method, corona discharge electrode-plasma jet method, parallel plate type, remote plasma type, atmospheric pressure plasma type, ICP type high density plasma. An apparatus employing a mold or the like can be exemplified.
The gas used for the plasma treatment is not particularly limited, and examples thereof include oxygen, nitrogen, rare gas (argon), hydrogen, and ammonia.

  The prepreg is a material for forming a fiber reinforced resin layer in which a matrix resin is impregnated in a reinforced fiber base material. When the matrix resin of the fiber reinforced resin layer is a cured product of a thermosetting resin, the matrix resin that impregnates the reinforcing fiber substrate in the prepreg is the thermosetting resin before curing.

  The thickness of the prepreg is preferably 10 μm to 5 mm, more preferably 30 μm to 3 mm, and particularly preferably 80 μm to 1 mm. However, the thickness of the prepreg can be appropriately set depending on the substrate.

  The temperature of the hot press is preferably equal to or higher than the melting temperature of the matrix resin contained in the prepreg, and the preferable range varies depending on the selected prepreg.

[Method of manufacturing printed circuit board]
The printed circuit board manufacturing method of the present invention is a method for obtaining a printed circuit board by forming a pattern circuit by etching the metal layer of the laminate of the present invention. The etching method for the metal layer is not particularly limited.

In the method of manufacturing a printed circuit board according to the present invention, after forming a pattern circuit by etching a metal layer, an interlayer insulating film may be formed on the pattern circuit, and a pattern circuit may be further formed on the interlayer insulating film. Good. The interlayer insulating film can be formed by, for example, the coating solution described above.
In the production of a printed circuit board, a solder resist may be laminated on the pattern circuit. The solder resist can be formed, for example, with the coating solution described above.
In the production of a printed circuit board, a cover lay film using a resin film such as a fluororesin film or a polyamide film may be laminated.

  The printed circuit board obtained by the manufacturing method of the present invention is used as a substrate for electronic devices such as radar, network routers, backplanes, and wireless infrastructures that require high-frequency characteristics, as well as various sensor substrates for automobiles and substrates for engine management sensors. This is useful, and is particularly suitable for applications aimed at reducing transmission loss in the millimeter wave band.

As described above, in the present invention, a curable fluororesin is used to form a cured product layer by ultraviolet irradiation or heating. Therefore, compared with the case of using a high-temperature fluororesin having a melting point of 260 ° C. or higher, a cured product layer having excellent adhesion with a metal layer, a prepreg, etc. can be formed without using special high-temperature equipment. Oxidation of the metal layer can also be suppressed. Moreover, since the curable fluororesin is used for the cured product layer and the adhesion of the cured product layer of the metal layer is excellent without roughening the surface of the metal layer, the obtained printed circuit board has excellent electrical characteristics, It can handle high-frequency frequencies.
Moreover, in this invention, the hardened | cured material layer excellent in especially adhesiveness with a metal layer, a prepreg, etc. can be formed by using the fluoropolymer F2 as a curable fluororesin. If the fluoropolymer F2 having a Tg of 5 ° C. or higher is used, a laminate having excellent adhesion between the cured product layer and the metal layer can be obtained even at a low temperature hot press of about 100 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following description.
[Peel strength at the interface between the cured product layer and the fiber reinforced resin layer]
A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the hot press laminate obtained in each example. The cured product layer and the fiber reinforced resin layer were peeled from one end in the length direction of the test piece to a position of 50 mm. Next, the test piece is peeled 90 degrees at a pulling speed of 50 mm / min using a tensile tester (Orientec Co., Ltd.) with the position 50 mm from one end in the length direction as the center, and the maximum load is peel strength ( N / cm). It shows that the adhesiveness of a hardened | cured material layer and a fiber reinforced resin layer is excellent, so that peeling strength is large.

[Peel strength at the interface between the cured product layer and the copper foil layer]
The cured product is the same as the measurement of the peel strength at the interface between the cured product layer and the fiber reinforced resin layer, except that the cured product layer and the copper foil layer are peeled from one end in the length direction of the test piece to a position of 50 mm. The peel strength (N / cm) at the interface between the layer and the copper foil layer was measured. It shows that the adhesiveness of a hardened | cured material layer and a copper foil layer is excellent, so that peeling strength is large.

[Production Example 1: Production of fluoropolymer]
A stainless steel autoclave with a stirrer having an internal volume of 1 L was degassed under reduced pressure, and then 2.23 g of a 50% by mass solution of Asahi Clin AK-225G (Asahi Glass Co., Ltd.) of perbutyl PV (manufactured by NOF Corporation), CF ₂ = CFOCF 50.5g of _{2 CF 2 CF 2 COOCH 3 (} MPVB), was charged with 790g of _{CF 2 = CFOCF 2 CF 2 CF} 3 (PPVE). Furthermore, after 90.0 g of CF ₂ = CF ₂ (TFE) was injected, the internal temperature was raised to 60 ° C. and polymerization was carried out for 4 hours. During this time, 60.0 g of TFE was further fed so that the pressure was maintained at 0.90 MPaG.

After cooling the autoclave and purging the gas, the contents were added to a glass beaker containing 3 kg of Asahi Clin AE-3000 (manufactured by Asahi Glass Co., Ltd.). After removing the upper layer, the lower monomer component was heated under reduced pressure to distill off the remaining monomer component, thereby obtaining 122.3 g of a fluoropolymer P1. The composition of the fluoropolymer P1 calculated by ¹ H-NMR and ¹⁹ F-NMR was MPVB unit: TFE unit: PPVE unit = 2: 68: 30 (molar ratio). The mass average molecular weight was 54,000. “MPVB unit” means a unit based on MPVB, and the same applies to other units.

[Production Example 2: Production of fluoropolymer]
26.5 g of the fluoropolymer P1 obtained in Production Example 1 was dissolved in 129.1 g of Asahiclin AC-2000, and then 4.0 g of methanol and 0.4 g of a 79% by mass aqueous solution of hydrazine monohydrate were added. The mixture was added and stirred at 40 ° C. for 6 hours. The reaction solution was transferred to a petri dish, preliminarily dried in the air, and then vacuum dried at 100 ° C. for 1 day to obtain a fluoropolymer F2-1. According to IR measurement, in the fluoropolymer F2-1, the absorption at 1,794 cm ⁻¹ based on C═O of the —COOCH ₃ group in the fluoropolymer P1 is almost halved, and based on the C═O of the —CONH group It was confirmed that a new absorption of 1,705 cm ⁻¹ occurred.

[Example 1]
Copper foil (electrolytic copper foil, manufactured by Mitsui Kinzoku Co., Ltd., product name “HS1-VSP”) with a solution containing a fluorine-containing polymer P1 which is a curable fluororesin at a solid content concentration of 10% by mass so as to have a thickness of 18 μm After being applied to the surface of the substrate and allowed to stand at room temperature for 0.5 hour, it was irradiated with ultraviolet rays (wavelength 254 nm) for 60 minutes in a nitrogen atmosphere to form a cured product layer having a thickness of 5 μm to obtain a single-sided copper-clad laminate. .

FR-4 (manufactured by Hitachi Chemical Co., Ltd., reinforcing fiber: glass fiber, matrix resin: epoxy resin, product name: GEA-67N, 0.2t (HAN), thickness on the cured layer side of the single-sided copper clad laminate. : 0.2 mm) was stacked and vacuum hot pressed under the conditions of a press temperature of 185 ° C., a press pressure of 3.0 MPa, and a press time of 60 minutes to obtain a hot press laminate H-1.
The peel strength at the interface between the cured product layer and the fiber reinforced resin layer in the obtained hot-press laminate H-1 was 6.7 N / cm.

The cured product layer sides of the two single-sided copper clad laminates were bonded together and hot pressed at a press temperature of 100 ° C., a press pressure of 3.0 MPa, and a press time of 60 minutes to obtain a hot press laminate H-2. . The interface strength between the cured product layer and the copper foil layer in the obtained hot press laminate H-2 was 15 N / cm.
A hot press laminate H-3 was obtained in the same manner as the hot press laminate H-2 except that the press temperature was 340 ° C. In the obtained hot press laminate H-3, the interface strength between the cured product layer and the copper foil layer was 15 N / cm.

[Example 2]
A single-sided copper clad laminate was obtained in the same manner as in Example 1 except that the fluoropolymer F2-1 was used instead of the fluoropolymer P1.
The cured product sides of the two single-sided copper-clad laminates were bonded together and hot pressed at a press temperature of 100 ° C., a press pressure of 3.0 MPa, and a press time of 60 minutes to obtain a hot press laminate H-4. In the obtained hot press laminate H-4, the interface strength between the cured product layer and the copper foil layer was 17 N / cm.
A hot press laminate H-5 was obtained in the same manner as the hot press laminate H-4 except that the pressing temperature was 340 ° C. The interface strength between the cured product layer and the copper foil layer in the obtained hot press laminate H-5 was 10 N / cm.

[Example 3]
After obtaining the single-sided copper clad laminated body like Example 1, the surface of the hardened | cured material layer was vacuum-plasma-processed. AP-1000 manufactured by NORDSON MARCH was used as the plasma processing apparatus. As plasma processing conditions, AP-1000 RF output is 300 W, the gap between the electrodes is 2 inches, the type of introduced gas is argon (Ar), the introduced gas flow rate is 50 cm ³ / min, the pressure is 13 Pa, and the treatment time is 1 minute. It was. A hot-press laminate H-6 was obtained in the same manner as the single-side copper-clad laminate H-1 of Example 1 except that the single-sided copper-clad laminate after the plasma treatment was used.
The peel strength at the interface between the cured product layer and the prepreg in the obtained hot press laminate H-6 was 12 N / cm.

Claims (19)

  The surface roughness Rz of the cured product layer made of a cured product of a resin material containing a curable fluororesin and the surface in contact with the cured product layer provided on one or both surfaces of the cured product layer is 4.5 μm or less. A laminate comprising a metal layer. The laminate according to claim 1, wherein the cured product layer has a water vapor transmission coefficient of 20 g · mm / m ² · day or less. The laminate according to claim 1 or 2, wherein the curable fluororesin comprises a fluoropolymer having a unit represented by the following formula U1.

(In the formula U1, X ¹ and X ² are each independently a hydrogen atom or a fluorine atom. Q ¹ is a single bond or an etheric oxygen atom. R ^f1 is a fluoroalkylene group, or It is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, Z ¹ is NR ¹ NR ² H, or NR ³ OR ^4. R ¹ , R ² , R ³ , R ⁴ is each independently a hydrogen atom or an alkyl group.) At least a part of the unit represented by the formula U1 is — [CF ₂ —CF (O (CF ₂ ) ₃ CONHNH ₂ )] — or — [CF ₂ —CF (O (CF ₂ ) ₃ CONHOH) —. The laminate according to claim 3, wherein   The laminate according to claim 3 or 4, wherein the fluoropolymer further has units based on fluoroethylene. The laminate according to any one of claims 3 to 5, wherein the fluoropolymer further has a unit represented by the following formula U2 (excluding a unit based on fluoroethylene).
^{- [CX 3 X 4 -CY 1} Y 2] - ··· formula U2
(However, in the formula U2, ^{X 3} and ^{X 4} each independently represent a hydrogen atom, .Y ¹ is a fluorine atom or a chlorine atom, .Y ² is a hydrogen atom, a fluorine atom or a chlorine atom, hydrogen An atom, a fluoroalkyl group, a fluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, a fluoroalkoxy group, or a fluoro having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms An alkoxy group.) The laminate according to any one of claims 3 to 6, wherein the fluoropolymer further has a unit represented by the following formula U3.

(In the formula U3, X ⁵ , X ⁶ and X ⁷ are each independently a fluorine atom or a hydrogen atom, two Q ² are each independently a single bond or an etheric oxygen atom, and R ^f2 is the number of carbon atoms. 1-6 fluoroalkylene groups, or C2-C25 fluoroalkylene groups having an etheric oxygen atom between carbon-carbon atoms.) The content of the group represented by -COZ ¹ of the fluoropolymer in is a 0.01~4.0mmol / g, the laminated body according to any one of claims 3-7.   9. The resin material according to claim 1, wherein the resin material further includes at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin curing agent. Laminated body.   The laminate according to any one of claims 1 to 9, wherein the resin material further includes a resin powder containing a fluororesin having a melting point of 260 to 380 ° C.   The melting point of the fluororesin contained in the resin powder having at least one adhesive 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 is 260 to 380. The laminate according to claim 10, which is an adhesive fluororesin at ° C.   Furthermore, the laminated body as described in any one of Claims 1-11 by which the fiber reinforced resin layer is joined to the surface on the opposite side to the said metal layer of the said hardened | cured material layer. A coating solution comprising a fluoropolymer having a unit represented by the following formula U1.

(In the formula U1, X ¹ and X ² are each independently a hydrogen atom or a fluorine atom. Q ¹ is a single bond or an etheric oxygen atom. R ^f1 is a fluoroalkylene group, or It is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, Z ¹ is NR ¹ NR ² H, or NR ³ OR ^4. R ¹ , R ² , R ³ , R ⁴ is each independently a hydrogen atom or an alkyl group.)   The coating liquid according to claim 13, further comprising at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin curing agent.   The coating liquid according to claim 13 or 14, further comprising a resin powder containing a fluororesin having a melting point of 260 to 380 ° C.   The melting point of the fluororesin contained in the resin powder having at least one adhesive 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 is 260 to 380. The coating liquid according to claim 15, which is an adhesive fluororesin at 0 ° C.   The coating liquid according to any one of claims 13 to 16 is applied to the surface of the metal layer to form a coating film, and the coating film is cured by one or both of ultraviolet irradiation and heating to obtain a cured product. The manufacturing method of the laminated body which forms a layer.   The manufacturing method of the laminated body of Claim 17 which joins a prepreg to the surface on the opposite side to the said metal layer of the said hardened | cured material layer by hot press.   The manufacturing method of a printed circuit board which forms a patterned circuit by etching the metal layer of the laminated body as described in any one of Claims 1-12, and obtains a printed circuit board.