TWI744379B - Metal laminated board, its manufacturing method, and printed circuit board manufacturing method - Google Patents

Abstract

The object of the present invention is to provide a metal laminated board, a method of manufacturing the same, and a method of manufacturing a printed circuit board, which can ensure excellent electrical characteristics while obtaining sufficient bonding strength between the insulating layer and the adhesive layer and between the adhesive layer and the conductive layer. A metal laminated board with an insulating layer, an adhesive layer, and a conductive layer. The insulating layer contains fluorine-containing resin resin powder. The resin powder contains particles (A) with a particle size of 10μm or more and does not contain particles larger than the insulating layer and the adhesive layer. For particles of total thickness, the surface roughness of the insulating layer provided with the adhesive layer is 0.5~3.0μm. And, a method of manufacturing a metal laminate and a method of manufacturing a printed circuit board using the metal laminate.

Description

Metal laminated board, its manufacturing method, and printed circuit board manufacturing method

The invention relates to a metal laminated board, a manufacturing method thereof, and a manufacturing method of a printed circuit board.

Background of the Invention In recent years, with the lightening, miniaturization, and high density of electronic products, the demand for various printed circuit boards has continued to expand. For the printed circuit board, for example, a metal laminate can be used, in which a conductive layer made of metal foil is laminated on an insulating layer made of an insulating material such as polyimide via an adhesive layer. The conductive layer of the metal laminate is patterned to form a circuit to form a printed circuit board. Recently, printed circuit boards are required to have excellent electrical characteristics (low dielectric constant, etc.) corresponding to frequencies in the high frequency band.

Regarding the part of the low dielectric constant that can be effectively used as the insulating layer of the printed circuit board, there are documents that propose a substrate containing fine fluoropolymer powder (resin powder) and polyimide. The fine fluoropolymer powder is made of polytetrafluoroethylene. It is composed of ethylene (PTFE) and has an average particle size of 0.02 to 5 μm (Patent Document 1). In addition, there are also documents that propose a substrate containing resin powder and thermosetting resin such as polyimide. The resin powder contains a fluorine-containing copolymer having functional groups such as carbonyl-containing groups and has an average particle size of 0.02-50μm ( Patent Document 2).

Prior Art Documents Patent Documents Patent Document 1: Japanese Patent Application Laid-Open No. 2005-142572 Patent Document 2: International Publication No. 2016/017801

SUMMARY OF THE INVENTION The problem to be solved by the invention, however, as a result of research by the inventors, it is found that the printed circuit board is composed of a laminate of insulating layer/adhesive layer/conductive layer or conductive layer/adhesive layer/insulating layer/adhesive layer/conductive layer Among them, when the substrates of Patent Documents 1 and 2 are used as the insulating layer, there may be cases where sufficient adhesion strength cannot be obtained between the insulating layer and the adhesive layer or between the adhesive layer and the conductive layer. Although reducing the resin powder content can improve the bonding strength between the aforementioned layers, it is difficult to ensure excellent electrical properties.

The object of the present invention is to provide a metal laminate that can ensure excellent electrical characteristics, and at the same time, obtain sufficient bonding strength between the insulating layer and the adhesive layer and between the adhesive layer and the conductive layer, and a method for manufacturing the metal laminate and a method for using the metal laminate Manufacturing method of printed circuit board.

Means to Solve the Problem The inventors of the present inventors have repeated intensive studies and found that the resin powder contained in the insulating layer contains particles with a particle size of 10 μm or more, and the surface of the insulating layer on the adhesive layer side can be appropriately roughened by anchoring. The effect improves the bonding strength between the insulating layer and the adhesive layer. In addition, controlling the particle size of the particles contained in the resin powder to the extent that the particles do not reach the gap between the adhesive layer and the conductive layer can prevent the adhesion of the adhesive layer and the conductive layer from being hindered by the resin powder. Adequate bonding strength is ensured between the bonding layer and the conductive layer. Based on these findings, the present invention has been completed.

The present invention has the following constitution. [1] A metal laminated board comprising: an insulating layer; an adhesive layer provided on at least one surface in the thickness direction of the insulating layer; and a conductive layer provided on the surface of the adhesive layer opposite to the insulating layer Above; The insulating layer contains a fluorine-containing resin resin powder, the resin powder contains particles with a particle size of 10 μm or more and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer, and the insulating layer is provided with the adhesive The surface roughness of the surface of the layer is 0.5~3.0μm. [2] The metal laminate as described in [1], wherein the content of particles with a particle diameter of 10 μm or more in the insulating layer is 5-18% by volume. [3] The metal laminate as described in [1] or [2], wherein the resin powder further contains particles with a particle size of less than 10 μm, and relative to the total volume of particles with a particle size of 10 μm or more and particles with a particle size of less than 10 μm (100% by volume), the content of particles with a particle diameter of 10μm or more is 8~63% by volume, and the content of particles with a particle diameter of less than 10μm is 37~92% by volume. [4] The metal laminate according to any one of [1] to [3], wherein the fluororesin is a fluorine-containing copolymer, which has a unit (1) having the following functional group and is mainly composed of tetrafluoroethylene The unit (2) has a melting point of 260-320°C, and the aforementioned functional group is selected from at least one functional group selected from the group consisting of a carbonyl-containing group, a hydroxyl group, an epoxy group, and an isocyanate group. [5] The metal laminate as described in [4], wherein the aforementioned fluorinated copolymer further has a unit (3-1) mainly composed of perfluoro(alkyl vinyl ether), and relative to the total amount of all units, The ratio of the aforementioned unit (1) is 0.01-3 mol%, the ratio of the aforementioned unit (2) is 90-99.89 mol%, and the ratio of the aforementioned unit (3-1) is 0.1-9.99 mol%. [6] The metal laminate as described in [4] or [5], wherein the fluorinated copolymer further has a unit (3-2) mainly composed of hexafluoropropylene, and relative to the total amount of all the units, the aforementioned unit The ratio of (1) is 0.01-3 mol%, the ratio of the aforementioned unit (2) is 90-99.89 mol%, and the ratio of the aforementioned unit (3-2) is 0.1-9.99 mol%. [7] The metal laminate according to any one of [4] to [6], wherein the aforementioned unit (1) comprises a unit containing a carbonyl group, and the aforementioned carbonyl group-containing group is selected from the carbon At least one of a group consisting of a group having a carbonyl group between atoms, a carbonate group, a carboxyl group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride residue. [8] The metal laminate according to any one of [1] to [7], wherein the relative dielectric constants of the insulating layer and the adhesive layer are both 2.1 to 3.5. [9] The metal laminate according to any one of [1] to [8], wherein the insulating layer further contains polyimide. [10] A method of manufacturing a metal laminated board, which is a method of manufacturing a metal laminated board as described in any one of [1] to [9]. A conductive layer is laminated on at least one surface in the thickness direction of the insulating layer; wherein the resin powder contains fluororesin and particles with a particle size of 10 μm or more, and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer particle.

[11] The method for manufacturing a metal laminated board as described in [10], which uses resin powder mixed with the following resin powders: resin powder (α) with a peak particle diameter of 10 to 100 μm; and a resin powder with a peak particle diameter of 0.3 to 8 μm Resin powder (β). [12] The method for manufacturing a metal laminate as described in [10] or [11], wherein at least one of the resin powder (α) and the resin powder (β) is a fluorinated copolymer, and the fluorinated copolymer It has a unit with the following functional groups (1) and a unit with tetrafluoroethylene as the main body (2), and the melting point is 260~320℃. The aforementioned functional groups are selected from carbonyl-containing groups, hydroxyl groups, and epoxy groups. And at least one functional group in the group consisting of isocyanate groups. [13] The method for manufacturing a metal laminate according to any one of [10] to [12], which uses a dispersion in which the resin powder has been dispersed in a liquid medium to form the insulating layer. [14] A method of manufacturing a printed circuit board, which is obtained by etching the aforementioned conductive layer of the metal laminate as described in any one of [1] to [9] to form a pattern circuit. [15] An insulating layer containing a fluorine-containing resin resin powder, and the resin powder in the insulating layer contains at least one of particles with a particle size of 10 μm or more and an aggregate with a particle size of 10 μm or more, and is relative to the formation of the insulating layer The total volume of the material, the content of the aforementioned particles and aggregates is 5-18% by volume. [16] The insulating layer according to [15], wherein the resin powder further contains particles with a particle size of less than 10 μm, and is relative to particles with a particle size of 10 μm or more, aggregates with a particle size of 10 μm or more, and particles with a particle size of less than 10 μm The total volume (100% by volume) of the above-mentioned particles with a particle size of 10μm or more and agglomerates with a particle size of 10μm or more is 8~63% by volume, and the content of particles with a particle size of less than 10μm is 37~92% by volume. [17] The insulating layer of [15] or [16], wherein the aforementioned fluororesin is a fluorine-containing copolymer, which has a unit with the following functional groups and a unit mainly composed of tetrafluoroethylene and has a melting point of 260-320°C The aforementioned functional group is at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, and an isocyanate group. [18] The insulating layer described in any one of Claims 15-17 has a relative dielectric constant of 2.1-3.5. [19] A method of manufacturing an insulating layer, which is a method of manufacturing an insulating layer as described in any one of [15] to [18], which is formed by using a dispersion in which resin powder has been dispersed in a liquid medium In the aforementioned insulating layer, the resin powder is mixed with the following powders: powder (a) with a peak particle diameter of 10-100 μm; and powder (b) with a peak particle diameter of 0.3-8 μm. [20] A metal laminated board comprising: an insulating layer; an adhesive layer provided on at least one surface in the thickness direction of the insulating layer; and a conductive layer provided on the surface of the adhesive layer opposite to the insulating layer Above; wherein, the aforementioned insulating layer is an insulating layer as described in any one of [15] to [18], and does not contain particles with a particle size exceeding the total thickness of the aforementioned insulating layer and the aforementioned adhesive layer and aggregates with a particle size of 10 μm or more Things. Invention effect

With the metal laminated board of the present invention, excellent electrical characteristics can be ensured, and at the same time, sufficient bonding strength can be obtained between the insulating layer and the adhesive layer and between the adhesive layer and the conductive layer. According to the method of manufacturing a metal laminate of the present invention, a metal laminate can be manufactured that can ensure excellent electrical characteristics and at the same time obtain sufficient bonding strength between the insulating layer and the adhesive layer and between the adhesive layer and the conductive layer. According to the manufacturing method of the printed circuit board of the present invention, it is possible to manufacture a printed circuit board that can ensure excellent electrical characteristics and at the same time obtain sufficient bonding strength between the insulating layer and the adhesive layer and between the adhesive layer and the conductive layer.

Modes for Implementing the Invention The following terms in this specification have the following meanings. "Surface roughness" is the value of the arithmetic average roughness of the surface of the coating film by measuring the height difference of the surface of the coating film by using the SURFCORDER (manufactured by Kosaka Laboratory Co., Ltd., model: ET200) of the height difference meter. "Relative Permittivity" is the value measured by SPDR (Split-Post Dielectric Resonator) method at a frequency of 2.5GHz under an environment in the range of 23℃±2℃ and 50±5%RH. . "Average particle size of resin powder" is the 50% cumulative diameter (D50) on a volume basis obtained by the laser diffraction scattering method. That is, the particle size distribution is measured by the laser diffraction scattering method, the total volume of the particle group is 100%, and the cumulative curve is obtained, and the particle size at the point where the cumulative volume is 50% on the cumulative curve. "The volume-based cumulative 90% diameter of resin powder (D90)" is the volume-based cumulative 90% diameter obtained by the laser diffraction scattering method. That is, the particle size distribution is measured by the laser diffraction scattering method, the total volume of the particle group is 100%, and the cumulative curve is obtained, and the particle size at the point where the cumulative volume is 90% on the cumulative curve. "Melt formable" means showing melt fluidity. "Showing melt fluidity" means that under the condition of loading 49N, there is a temperature with a melt flow rate of 0.1 to 1000 g/10 minutes at a temperature higher than the melting point of the resin by 20°C or more. The "melt flow rate" is the melt mass flow rate (MFR) specified in JIS K 7210: 1999 (ISO 1133: 1997). The "unit" of the polymer means the atomic group derived from 1 molecule of the monomer formed by the polymerization of the monomer. The unit may be an atomic group directly formed by a polymerization reaction, or may be an atomic group in which a part of the atomic group is converted into another structure by processing the polymer obtained by the polymerization reaction. "(Meth)acrylate" is the general term for acrylate and methacrylate. In addition, "(meth)acryloyl" is a general term for acrylic and methacryloyl. "Heat-resistant resin" is a polymer compound with a melting point of 280°C or higher, or a polymer compound with a maximum continuous use temperature of 121°C or higher as specified in JIS C 4003:2010 (IEC 60085:2007).

[Metal Laminate] The metal laminate of the present invention includes: an insulating layer; an adhesive layer provided on at least one surface in the thickness direction of the insulating layer; and a conductive layer provided on the adhesive layer opposite to the insulating layer On the surface of the side and made of metal. The adhesive layer and the conductive layer in the metal laminated board of the present invention can be provided on only one side in the thickness direction of the insulating layer, or can be provided on both sides in the thickness direction of the insulating layer. The laminated structure of the metal laminate of the present invention can include a laminated structure in which an insulating layer, an adhesive layer, and a conductive layer are sequentially laminated (also denoted as "insulating layer/adhesive layer/conductive layer", the same below), and conductive layer/adhesive Layer/insulating layer/adhesive layer/conductive layer.

For the insulating layer, for example, a film or a fiber reinforced film can be used. The resin used in the film may be a thermoplastic resin or a cured product of a thermosetting resin, and a heat-resistant resin is preferred.

Heat-resistant resins can include polyimides (aromatic polyimides, etc.), polyarylates, polysulfides, polyarylsulfites (polyethersulfides, etc.), aromatic polyamides, and aromatic polyether amides. , Polyphenylene sulfide, polyaryl ether ketone, polyamide imide, liquid crystal polyester, epoxy resin, acrylic resin, phenol resin, polyester resin, bismaleimide resin, polyolefin resin, modified Quality polyphenylene ether resin, fluororesin, etc. Among them, the heat-resistant resin is preferably polyimide. The heat-resistant resin may be used individually by 1 type, or may use 2 or more types.

The resin forming the film preferably has a reactive group (ii) capable of reacting with the functional group (i) described later. Examples of the reactive group (ii) include a carbonyl group-containing group, a hydroxyl group, an amino group, and an epoxy group. Polyimide film is particularly suitable for the insulating layer.

The fiber-reinforced film is a film containing a reinforced fiber base material and a cured product of thermoplastic resin or thermosetting resin. The reinforcing fibers used in the fiber-reinforced film include glass fibers, aramid fibers, and carbon fibers. Reinforcing fibers can be surface-treated. The reinforcing fiber may be used singly or in combination of two or more kinds.

From the viewpoint of the mechanical properties of the fiber-reinforced film, the shape of the fiber-reinforced substrate is preferably processed into a sheet. Specifically, for example, a fabric formed by woven reinforcing fiber bundles composed of a plurality of reinforcing fibers, a base material in which a plurality of reinforcing fibers are tightly bundled in one direction, and those formed by stacking the same can be mentioned. The reinforced fiber does not need to be continuous over the entire length of the reinforced fiber sheet or the entire width of the width direction, and can be cut off in the middle.

In the present invention, the insulating layer contains resin powder. Specifically, for example, the insulating layer can be made into a thin film containing resin powder. The resin powder contains fluororesin as an essential ingredient, and other resins other than fluororesin can be included on demand.

The fluororesin forming the resin powder is not particularly limited, and examples include polytetrafluoroethylene (hereinafter referred to as "PTFE"), tetrafluoroethylene (hereinafter referred to as "TFE")/fluoroalkyl vinyl ether copolymer, TFE/ Hexafluoropropylene copolymer, ethylene/TFE copolymer, etc. The fluororesin forming the resin powder may be used singly or in two or more types.

From the point of view of adhesion, the fluororesin forming the resin powder preferably has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, and an isocyanate group (hereinafter also referred to as "functional Group (i)"), and a fluorinated copolymer (1) with a functional group (i) and a unit with TFE as the main body (hereinafter also referred to as "TFE unit") and a melting point of 260-320°C ( X) (hereinafter referred to as polymer (X)) is preferred.

Polymer (X) can also have units other than unit (1) and TFE unit according to demand. Unit (1) and units other than TFE unit are preferably perfluorinated units such as PAVE unit or HFP unit described later.

The carbonyl group-containing group in the functional group (i) is not particularly limited as long as it is a group containing a carbonyl group in the structure, and examples include groups formed by having a carbonyl group between the carbon atoms of the hydrocarbon group, carbonate groups, carboxyl groups, and halogenated groups. Formaldehyde, alkoxycarbonyl, acid anhydride residues, polyfluoroalkoxycarbonyl, fatty acid residues, etc. Among them, from the viewpoint of improving mechanical pulverization and adhesion, a group composed of a carbonyl group between the carbon atoms of a hydrocarbon group, a carbonate group, a carboxyl group, a halogenated methanoyl group, an alkoxycarbonyl group, or an acid anhydride residue Preferably, a carboxyl group or an acid anhydride residue is preferred.

Examples of the group formed by having a carbonyl group between the carbon atoms of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms. The number of carbon atoms of the alkylene group refers to the number of carbon atoms of the part other than the carbonyl group in the alkylene group. The alkylene group may be linear or branched. The haloformyl group is a group represented by -C(=O)-X (except, X is a halogen atom). Examples of the halogen atom of the haloformyl group include a fluorine atom, a chlorine atom, etc., and a fluorine atom is preferred. That is, the haloformyl group is preferably a fluoroformyl group (also called a fluorocarbonyl group). The alkoxy group of the alkoxycarbonyl group may be linear or branched. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and a methoxy group or an ethoxy group is particularly preferable.

The unit (1) is preferably a unit mainly composed of a monomer having a functional group (i) (hereinafter also referred to as "monomer (m1)"). The functional group (i) possessed by the monomer (m1) may be one or two or more. When the monomer (m1) has two or more functional groups (i), these functional groups (i) may be the same or different from each other. The monomer (m1) is preferably a compound having one functional group (i) and one polymerizable double bond. A monomer (m1) may be used individually by 1 type, and may use 2 or more types together.

The monomer having a carbonyl group-containing group in the monomer (m1) may include, for example, a cyclic hydrocarbon compound having an acid anhydride residue and a polymerizable unsaturated bond (hereinafter also referred to as "monomer (m11)"), a monomer having a carboxyl group Body (hereinafter also referred to as "monomer (m12)"), vinyl ester, (meth)acrylate, CF ₂ =CFOR ^{f1 COOX 1} (However, R ^f1 is the number of carbon atoms 1~ 10 perfluoroalkylene, X ¹ is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms), etc.

The monomer (m11) can be exemplified by an anhydride of unsaturated dicarboxylic acid and the like. Anhydrides of unsaturated dicarboxylic acids include itaconic anhydride (hereinafter also referred to as "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2,3-dicarboxylic anhydride (alias: Nadic acid anhydride, hereinafter also referred to as "NAH"), maleic anhydride, etc. Monomers (m12) include unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, and maleic acid; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid Sour etc. Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl trimethyl acetate, vinyl benzoate, and the like. Examples of (meth)acrylates include (polyfluoroalkyl)acrylate, (polyfluoroalkyl)methacrylate, and the like.

Monomers having a hydroxyl group include vinyl esters, vinyl ethers, allyl ethers, unsaturated carboxylic acid esters ((meth)acrylate, crotonate, etc.) and have 1 at the end or side chain. Compounds with more than one hydroxyl group, unsaturated alcohols. Specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl crotonic acid, and allyl alcohol. Examples of monomers with epoxy groups include unsaturated glycidyl ethers (allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.) And unsaturated glycidyl esters (glycidyl acrylate, glycidyl methacrylate, etc.). Monomers having isocyanate groups include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, 1,1-bis( (Meth)acryloyloxymethyl)ethyl isocyanate and the like.

From the standpoint of improving mechanical pulverization properties and improving adhesion to metals, the unit (1) preferably has at least a carbonyl group-containing group as the functional group (i). The monomer (m1) is preferably a monomer having a carbonyl group-containing group.

From the viewpoint of thermal stability and improved adhesion, the monomer having a carbonyl group-containing group is preferably the monomer (m11). Among them, IAH, CAH or NAH is particularly preferred. If at least one selected from the group consisting of IAH, CAH and NAH is used, there is no need to use the special polymerization method required when maleic anhydride is used (refer to Japanese Patent Laid-Open No. 11-193312), and it can be easily To produce fluorinated copolymers containing acid anhydride residues. Among them, NAH is preferred from the viewpoint of superior adhesion to thermoplastic resins and the like.

The polymer (X) may also have a unit with perfluoro(alkyl vinyl ether) (hereinafter also referred to as “PAVE”) as the main body (hereinafter also referred to as “PAVE unit”) as the unit (1) and units other than the TFE unit .

PAVE can be exemplified by CF ₂ =CFOR ^f2 (However, R ^f2 is a perfluoroalkyl group with 1 to 10 carbon atoms that may contain ethereal oxygen atoms). The ^{perfluoroalkyl group in R f2} may be linear or branched. The ^{number of carbon atoms of R f2} is preferably 1~3. CF ₂ =CFOR ^f2 can be exemplified as CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ =CFOCF ₂ CF ₂ CF ₂ CF _3. CF ₂ =CFO(CF ₂ ) ₈ F, etc., PPVE is suitable. PAVE can be used alone or in combination of two or more.

The polymer (X) may have a unit mainly composed of hexafluoropropylene (hereinafter also referred to as "HFP") (hereinafter referred to as "HFP unit") as units other than the unit (1) and the TFE unit.

The polymer (X) may have units other than the "PAVE unit" and the "HFP unit" (hereinafter referred to as "other units") as units other than the unit (1) and the TFE unit.

Other units can include, for example, fluorine-containing monomers (except for monomer (m1), TFE, PAVE and HFP) as the main body and non-fluorine-containing monomers (except for monomer (m1)) as the main body. unit.

茂烷)等。該等可單獨使用1種或可使用2種以上。The aforementioned fluorine-containing monomer is preferably a fluorine-containing compound having a polymerizable double bond, such as fluoroolefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (except for TFE and HFP) 、CF ₂ =CFOR ^f3 SO ₂ X ³ (However, R ^f3 is a perfluoroalkylene group with 1 to 10 carbon atoms or a perfluoroalkylene group with 2 to 10 carbon atoms containing an etheric oxygen atom, X ³ Is a halogen atom or a hydroxyl group), CF ₂ =CF(CF ₂ ) _p OCF=CF ₂ (but p is 1 or 2), CH ₂ =CX ⁴ (CF ₂ ) _q X ⁵ (but X ⁴ is a hydrogen atom Or fluorine atom, q is an integer of 2-10, X ⁵ is hydrogen atom or fluorine atom), perfluoro (2-methylene-4-methyl-1,3-di

Methylene) and so on. These may be used individually by 1 type, or may use 2 or more types.

The aforementioned fluorine-containing monomer is preferably vinylidene fluoride, chlorotrifluoroethylene or CH ₂ =CX ⁴ (CF ₂ ) _q X ⁵ . CH ₂ =CX ⁴ (CF ₂ ) _q X ⁵ can be, for example, 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, etc., and CH ₂ =CH(CF ₂ ) ₄ F or CH ₂ =CH(CF ₂ ) ₂ F is suitable.

The aforementioned non-fluorine-containing monomer is preferably a non-fluorine-containing compound having one polymerizable double bond, and examples thereof include olefins with 3 or less carbon atoms such as ethylene and propylene. These may be used individually by 1 type, or may use 2 or more types. The monomer (m42) is preferably ethylene or propylene, and ethylene is particularly preferred.

The said fluorine-containing monomer and the said non-fluorine-containing monomer may be used individually by 1 type, respectively, or may use 2 or more types together. Or, the aforementioned fluorine-containing monomer and the aforementioned non-fluorine-containing monomer may be used in combination.

The polymer (X) is preferably a copolymer (X-1) or a copolymer (X-2) described later, and a copolymer (X-1) is particularly preferred.

Copolymer (X-1) is a copolymer having unit (1), TFE unit and PAVE unit. The ratio of unit (1) is preferably 0.01-3 mol%, and the ratio of TFE unit is 90 relative to the total of all units. ~99.89 mol%, PAVE unit ratio is 0.1~9.99 mol%.

The copolymer (X-1) can have at least one of the HFP unit and other units according to demand. Copolymer (X-1) can be composed of unit (1), TFE unit and PAVE unit, can be composed of unit (1), TFE unit, PAVE unit and HFP unit, and can be composed of unit (1), TFE unit, PAVE unit and Other units can also be composed of unit (1), TFE unit, PAVE unit, HFP unit, and other units.

The copolymer (X-1) is preferably a copolymer having a monomer containing a carbonyl group-containing group as the main unit, a TFE unit and a PAVE unit, and a copolymer having a monomer (m11) as the main unit, a TFE unit Copolymers with PAVE units are particularly preferred. Desirable specific examples of the copolymer (X-1) include TFE/PPVE/NAH copolymer, TFE/PPVE/IAH copolymer, TFE/PPVE/CAH copolymer, and the like.

The copolymer (X-1) may have a functional group (i) as a terminal group. The functional group (i) can be introduced by appropriately selecting the radical polymerization initiator, chain transfer agent, etc. used in the production of the copolymer (X-1).

Relative to the total of all units constituting the copolymer (X-1), the unit (1) ratio is 0.01 to 3 mol%, preferably 0.03 to 2 mol%, and more preferably 0.05 to 1 mol%. If the content of the unit (1) is more than the lower limit of the aforementioned range, it is easy to obtain a resin powder with a high bulk density. In addition, the adhesion between the resin powder and the thermoplastic resin, etc., and the interlayer adhesion between the film formed of a dispersion or liquid composition and other substrates (metals, etc.) are good. If the content of the unit (1) is below the upper limit of the aforementioned range, the heat resistance and color tone of the copolymer (X-1) will be better.

With respect to the total of all units constituting the copolymer (X-1), the TFE unit ratio is 90-99.89 mol%, preferably 95-99.47 mol%, and 96-98.95 mol% is particularly preferred. If the content of the TFE unit is above the lower limit of the aforementioned range, the electrical properties (low dielectric constant, etc.), heat resistance, chemical resistance, etc. of the copolymer (X-1) are better. If the content of the TFE unit is below the upper limit of the aforementioned range, the melt formability and stress cracking resistance of the copolymer (X-1) will be better.

Relative to the total of all units constituting the copolymer (X-1), the PAVE unit ratio is 0.1 to 9.99 mol%, preferably 0.5 to 9.97 mol%, and particularly preferably 1 to 9.95 mol%. If the content of the PAVE unit is within the aforementioned range, the formability of the copolymer (X-1) is better.

Relative to the total of all units in the copolymer (X-1), the total ratio of units (1), TFE units and PAVE units is preferably 90 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more good. The upper limit of the ratio is not particularly limited, and it may be 100 mol%.

The content of each unit in the copolymer (X-1) can be measured by NMR analysis such as melting nuclear magnetic resonance (NMR) analysis, fluorine content analysis, infrared absorption spectrum analysis, and the like. For example, as described in Japanese Patent Application Laid-Open No. 2007-314720, the ratio (mol %) of the unit (1) in all the units constituting the copolymer (X-1) can be obtained using methods such as infrared absorption spectroscopy.

Copolymer (X-2) is a copolymer having unit (1), TFE unit and HFP unit (except for copolymer (X-1)), in which the ratio of unit (1) is 0.01 relative to the total of all units ~3 mol%, TFE unit ratio is 90~99.89 mol%, HFP unit ratio is 0.1~9.99 mol%.

The copolymer (X-2) can also have PAVE units and other units according to demand. Copolymer (X-2) can be composed of unit (1), TFE unit and HFP unit, and can be composed of unit (1), TFE unit, HFP unit and PAVE unit (except for copolymer (X-1)), It can be composed of unit (1), TFE unit, HFP unit and other units, and can also be composed of unit (1), TFE unit, HFP unit, PAVE unit and other units (except for copolymer (X-1)).

The copolymer (X-2) is preferably a copolymer having a monomer containing a carbonyl group-containing group as the main unit, a TFE unit and a HFP unit, and a monomer (m11) as the main unit, a TFE unit and HFP Copolymers of units are particularly preferred. Desirable specific examples of the copolymer (X-2) include TFE/HFP/NAH copolymers, TFE/HFP/IAH copolymers, TFE/HFP/CAH copolymers, and the like. In addition, the polymer (X-2) may have a terminal group having a functional group (i) similarly to the polymer (X-1).

Relative to the total of all units constituting the copolymer (X-2), the unit (1) ratio is 0.01 to 3 mol%, preferably 0.02 to 2 mol%, and more preferably 0.05 to 1.5 mol%. If the content of the unit (1) is more than the lower limit of the aforementioned range, it is easy to obtain a resin powder with a high bulk density. In addition, the adhesion between the resin powder and the thermoplastic resin, etc., and the interlayer adhesion between the film formed of a dispersion or liquid composition and other substrates (metals, etc.) are good. If the content of the unit (1) is below the upper limit of the aforementioned range, the heat resistance and color tone of the copolymer (X-2) will be better.

Relative to the total of all units constituting the copolymer (X-2), the TFE unit ratio is 90-99.89 mol%, preferably 91-98 mol%, and particularly preferably 92-96 mol%. If the content of the TFE unit is above the lower limit of the aforementioned range, the electrical properties (low dielectric constant, etc.), heat resistance, chemical resistance, etc. of the copolymer (X-2) will be better. If the content of the TFE unit is below the upper limit of the aforementioned range, the melt formability and stress cracking resistance of the copolymer (X-2) will be better.

With respect to the total of all units constituting the copolymer (X-2), the HFP unit ratio is 0.1 to 9.99 mol%, preferably 1 to 9 mol%, and particularly preferably 2 to 8 mol%. If the content of the HFP unit is within the aforementioned range, the formability of the copolymer (X-2) is better.

Relative to the total of all units in the copolymer (X-2), the total ratio of unit (1), TFE unit and HFP unit is preferably 90 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more good. The upper limit of the ratio is not particularly limited, and it may be 100 mol%.

The melting point of the polymer (X) is preferably 260-320°C, preferably 280-320°C, more preferably 295-315°C, and particularly preferably 295-310°C. If the melting point of the polymer (X) is above the lower limit of the above range, the heat resistance is better. If the melting point of the polymer (X) is below the upper limit of the above range, the melt moldability is good. In addition, the melting point of the polymer (X) can be adjusted by the type, content ratio, molecular weight, etc. of the unit constituting the polymer (X). For example, the higher the ratio of TFE units, the higher the melting point. Preferably, the polymer (X) can be melt-formed.

The melt flow rate (MFR) of the polymer (X) is preferably 0.1 to 1000 g/10 minutes, 0.5 to 100 g/10 minutes is preferred, 1 to 30 g/10 minutes is more preferred, and 5 to 20 g/10 minutes is particularly preferred. If the MFR is more than the lower limit of the above range, the molding processability of the polymer (X) is good, and the surface smoothness and appearance of a film formed using a dispersion or a liquid composition are good. If the MFR is below the upper limit of the above range, the mechanical strength of the polymer (X) is good, and the mechanical strength of a film formed by using a dispersion or a liquid composition is good.

The molecular weight scale of the MFR-based polymer (X), a large MFR indicates a small molecular weight, and a small MFR indicates a large molecular weight. The molecular weight and MFR of the polymer (X) can be adjusted by the production conditions of the polymer (X). For example, shortening the polymerization time during the polymerization of monomers tends to increase the MFR.

The relative dielectric constant of the polymer (X) is preferably 2.5 or less, and preferably 2.4 or less, and particularly preferably 2.0 to 2.4. The lower the relative permittivity of the polymer (X), the better the electrical properties of the thin film formed using the dispersion or liquid composition. For example, when the thin film is used as the substrate of a printed circuit board, excellent transmission efficiency can be obtained . The relative dielectric constant of the polymer (X) can be adjusted through the content of TFE units.

The polymer (X) can be produced by a conventional method. The method for producing the polymer (X) can be exemplified by the method described in paragraphs [0053] to [0060] of International Publication No. 2016/017801.

Resins other than fluororesins are not particularly limited as long as they do not impair electrical reliability, and examples include aromatic polyesters, polyamides, and thermoplastic polyimines. The other resins may be used singly or in two or more types.

The resin powder preferably contains fluororesin as the main component, preferably polymer (X) as the main component. If the polymer (X) is the main component, it is easy to obtain a resin powder with a high bulk density. The greater the bulk density of the resin powder, the better the handling. In addition, the resin powder having "polymer (X) as the main component" means that the ratio of the polymer (X) is 80% by mass or more with respect to the total amount (100% by mass) of the resin powder. Relative to the total amount of resin powder (100% by mass), the ratio of the polymer (X) is preferably 85% by mass or more, preferably 90% by mass or more, and more preferably 100% by mass.

The resin powder contains particles with a particle size of 10 μm or more (hereinafter also referred to as "particles (A)") and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer. By containing particles (A) in the resin powder, the surface of the insulating layer can be appropriately roughened, and an anchoring effect is exhibited between the insulating layer and the adhesive layer, thereby increasing the adhesive strength between the layers. In addition, the resin powder does not contain particles having a particle size exceeding the total thickness of the insulating layer and the adhesive layer, which can prevent the resin powder from reaching the gap between the adhesive layer and the conductive layer. Thereby, it is possible to prevent the adhesion between the adhesive layer and the conductive layer from being hindered by the resin powder of the fluorine-containing resin, so that sufficient adhesive strength can be obtained between the layers. In addition, when an adhesive layer is provided on both sides of the insulating layer, "particles with a particle diameter exceeding the total thickness of the insulating layer and the adhesive layer" means the thickness of the insulating layer and the thickness of the adhesive layer. Total value. When the adhesive layer with different thickness is provided on both sides of the insulating layer, the thickness of the adhesive layer with the thinner thickness is used as the reference.

The particle size of the particles (A) is 10 μm or more and does not exceed the total thickness of the insulating layer and the adhesive layer. The upper limit of the particle size of the particles (A) can be appropriately set according to the total thickness of the insulating layer and the adhesive layer, and is preferably 100 μm, preferably 80 μm, and particularly preferably 40 μm.

From the viewpoint of excellent dispersion stability in the liquid during the film manufacturing process, the resin powder preferably contains particles with a particle size of less than 10 μm (hereinafter also referred to as "particles (B)") in addition to the particles (A). The lower limit of the particle (B) is preferably 0.01 μm, preferably 0.1 μm.

Relative to the total volume of the material forming the insulating layer, the resin powder content in the insulating layer is preferably 5 to 80% by volume, preferably 7 to 50% by volume, and particularly preferably 10 to 45% by volume. If the resin powder content is more than the lower limit of the aforementioned range, it is easy to obtain excellent electrical properties, and it is easy to exhibit an anchoring effect between the insulating layer and the adhesive layer. If the content of the resin powder is below the upper limit of the aforementioned range, the reduction in mechanical strength such as the tensile strength of the film at room temperature and heating can be suppressed, and a film with sufficient strength can be obtained.

Relative to the total volume of the material forming the insulating layer, the content of particles (A) in the insulating layer is preferably 5-18% by volume, preferably 6-15% by volume. If the content of the particles (A) is more than the lower limit of the aforementioned range, it is easy to obtain excellent electrical properties, and it is easy to develop an anchoring effect between the insulating layer and the adhesive layer. If the content of the particles (A) is below the upper limit of the aforementioned range, the reduction in mechanical strength such as the tensile strength of the film at room temperature and heating can be suppressed, and a film with sufficient strength can be obtained.

When the resin powder contains particles (A) and particles (B), the content of particles (A) should be 8~63% by volume and the content of particles (B) should be 37~92% by volume, and the content of particles (A) should be 8~60% by volume. % And the content of particles (B) is preferably 40-92% by volume, more preferably the content of particles (A) is 13-55 vol% and the content of particles (B) is 45-87 vol%. In addition, the total volume of particles (A) and particles (B) is 100% by volume.

In addition, the insulating layer contains particles (A), that is, particles with a particle size of 10 μm or more, and may also contain aggregates and particles (A) with a particle size of 10 μm or more, or instead of the particles (A). Aggregate is a structure formed by agglomeration of many particles, that is, when the cut-off insulating layer is observed with a scanning electron microscope, it can be seen that two or more particles are adjacent to one another. However, if the surface roughness of the insulating layer is not specified to be 0.5~3.0μm, relative to the total volume of the material forming the insulating layer, the insulating layer contains the aforementioned particles (A) and aggregates with a particle size of 10μm or more. The total amount is 5-18% by volume.

The manufacturing method of resin powder can be exemplified by the following method: if necessary, the powder material containing fluororesin is pulverized and then classified (sieved, etc.) to obtain particles (A) without a particle size larger than that of the insulating layer and the adhesive layer. Resin powder of particles with total thickness. When the fluororesin is produced by solution polymerization, suspension polymerization, or emulsion polymerization, after removing the organic solvent or aqueous medium used for polymerization and recovering the granular fluororesin, it is pulverized or classified (sieved, etc.). When the fluororesin obtained by polymerization contains particles (A) and does not contain particles having a particle size exceeding the total thickness of the insulating layer and the adhesive layer, the fluororesin can be used as a resin powder as it is. When two or more kinds of resins are used as the powder material, it is preferable to melt and knead the resins before pulverizing and classifying them. In addition, two or more types of resin powders with different particle size distributions may be mixed.

The pulverization method and classification method of the powder material can adopt the method described in paragraphs [0065]~[0069] of International Publication No. 2016/017801. In addition, as far as resin powder is concerned, if there is a resin powder that meets expectations on the market, it can also be used.

The surface roughness of the side where the insulating layer is provided with the adhesive layer is 0.5 to 3.0 μm, preferably 0.5 to 2.5 μm, and preferably 0.5 to 2.0 μm. If the aforementioned surface roughness is more than the lower limit of the aforementioned range, the anchoring effect can be fully exhibited between the insulating layer and the adhesive layer, and sufficient adhesive strength can be obtained. If the surface roughness is below the upper limit of the aforementioned range, the reduction in mechanical strength such as the tensile strength of the film at room temperature and heating can be suppressed, and a film with sufficient strength can be obtained.

The insulating layer may also contain well-known additives as required. Examples of additives include fillers. The insulating layer contains fillers, which can reduce the dielectric constant or dielectric tangent of the insulating layer. The filler is preferably an inorganic filler, such as those described in paragraph [0089] of International Publication No. 2016/017801. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

When the insulating layer contains fillers, relative to 100 parts by mass of the resin powder, the filler content in the insulating layer is preferably 0.1~300 parts by mass, preferably 1~200 parts by mass, more preferably 3~150 parts by mass, especially 5~100 parts by mass Good, 10~60 parts by mass is the best. The more filler content, the lower the coefficient of linear expansion (CTE) of the insulating layer, and the better the thermal dimension of the insulating layer.

The thickness of the insulating layer is preferably 4 to 1000 μm, preferably 6 to 300 μm, and particularly preferably 7 to 50 μm. If the thickness of the insulating layer is more than the lower limit of the aforementioned range, the printed board is not easily deformed excessively, and therefore the conductive layer is not easily broken. If the thickness of the insulating layer is less than the upper limit of the aforementioned range, flexibility is good, and it can respond to the miniaturization and weight reduction of the printed circuit board.

The relative dielectric constant of the insulating layer is preferably 2.1~3.5, and 2.1~3.3 is particularly preferred. If the relative dielectric constant of the insulating layer is below the upper limit of the aforementioned range, it is advantageous to require a printed circuit board with a low dielectric constant. If the relative dielectric constant is above the lower limit of the aforementioned range, both electrical characteristics and adhesiveness are good.

The material for forming the adhesive layer can be, for example, thermoplastic resin. Among them, thermoplastic polyimide (hereinafter also referred to as "TPI") is suitable. The material for forming the adhesive layer may be used singly, or two or more kinds may be used.

The thickness of the subsequent layer is preferably 3-100 μm, and preferably 3-50 μm. If the thickness of the subsequent layer is above the lower limit of the aforementioned range, the bonding strength with the conductive layer and the insulating layer is better. If the thickness of the subsequent layer is less than the upper limit of the aforementioned range, the electrical properties are better. When forming adhesive layers on both sides of the insulating layer, the composition and thickness of each adhesive layer can be the same or different. From the viewpoint of easily suppressing warpage, it is preferable to make the composition and thickness of each adhesive layer the same.

The relative dielectric constant of the subsequent layer is preferably 2.1 to 3.5, and 2.1 to 3.0 is particularly preferred. If the relative dielectric constant of the insulating layer is below the upper limit of the aforementioned range, it is advantageous to require a printed circuit board with a low dielectric constant. If the relative dielectric constant is above the lower limit of the aforementioned range, both electrical characteristics and adhesiveness are good.

The metal constituting the conductive layer can be appropriately selected depending on the application, and examples include copper or copper alloys, stainless steel or alloys thereof. The conductive layer is preferably metal foil, and copper foil such as rolled copper foil and electrolytic copper foil is preferred. A rust preventive layer (for example, an oxide film of chromate, etc.) or a heat-resistant layer may be formed on the surface of the metal foil. In addition, in order to improve the adhesion with the adhesive layer, a coupling agent treatment or the like may be applied to the surface of the metal foil.

The thickness of the conductive layer is not particularly limited. It is sufficient to select a thickness that can fully function according to the purpose of the metal laminate, preferably 0.1-50μm, more preferably 1-25μm, and more preferably 2-25μm.

The embodiment of the metal laminated board of the present invention can be the metal laminated board 1 as illustrated in FIG. 1. The metal laminate 1 includes an insulating layer 10, an adhesive layer 12, and a conductive layer 14. The adhesive layer 12 is provided on a surface 10a in the thickness direction of the insulating layer 10, and the conductive layer 14 is provided on the adhesive layer 12 opposite to the insulating layer 10 On the side. The insulating layer 10 contains resin powder 16, and this resin powder 16 contains particle (A) 16a and particle (B) 16b. A part of the resin powder 16 partially protrudes from the surface 10a of the insulating layer 10 on the adhesive layer 12 side. Thereby, the surface roughness of the surface 10a of the insulating layer 10 is 0.5 to 3.0 μm. The resin powder 16 does not contain particles having a particle size exceeding the total thickness d1+d2 (μm) of the insulating layer 10 and the adhesive layer 12.

Another embodiment of the metal laminated board of the present invention can be the metal laminated board 2 as illustrated in FIG. 2. The metal laminate 2 includes an insulating layer 20, a first adhesive layer 22, a first conductive layer 24, a second adhesive layer 26, and a second conductive layer 28. The first adhesive layer 22 is provided on one surface in the thickness direction of the insulating layer 20 On 20a, the first conductive layer 24 is provided on the side opposite to the insulating layer 20 of the first adhesive layer 22, and the second adhesive layer 26 is provided on the other surface 20b in the thickness direction of the insulating layer 20. The second conductive layer 28 is provided on the side opposite to the insulating layer 20 of the second adhesive layer 26. The insulating layer 20 contains the resin powder 30, and this resin powder 30 contains the particle (A) 30a and the particle (B) 30b. Part of the resin powder 30 partially protrudes from the two surfaces 20a, 20b of the insulating layer 20, respectively. Thereby, the surface roughness of the surface 20a and the surface 20b of the insulating layer 20 are respectively 0.5-3.0 μm. The resin powder 30 does not contain particles having a particle size exceeding the total thickness d3+d4 of the insulating layer 20 and the first adhesive layer 22, or the total thickness d3+d5 of the insulating layer 20 and the second adhesive layer 26, which is smaller.

In the metal laminated board of the present invention described above, the insulating layer contains resin powder of fluorine-containing resin. Therefore, the dielectric constant and dielectric tangent are low, and the electrical characteristics are excellent. In addition, since at least a part of the particles (A) contained in the resin powder partially protrudes on the surface of the insulating layer on the adhesive layer side, the surface roughness of the insulating layer on the adhesive layer side is 0.5 to 3.0 μm. Thereby, an anchoring effect can be exhibited between the insulating layer and the adhesive layer, and therefore, the adhesive strength between the insulating layer and the adhesive layer can be sufficiently improved. In addition, the adhesive strength between the adhesive layer and the conductive layer is greater than the adhesive strength between the fluorine-containing resin resin powder and the conductive layer. Therefore, if the resin powder reaches between the bonding layer and the conductive layer, it will hinder the bonding between the bonding layer and the conductive layer. However, in the metal laminated board of the present invention, the resin powder does not contain particles having a particle size exceeding the total thickness of the insulating layer and the adhesive layer, so that the resin powder can be prevented from reaching the gap between the adhesive layer and the conductive layer. Therefore, sufficient bonding strength can be ensured between the bonding layer and the conductive layer.

[Method of Manufacturing Metal Laminated Sheet] The method of manufacturing the metal laminated sheet of the present invention will be described below. The manufacturing method of the metal laminated board of the present invention has the following steps 1 and 2. Step 1: Use resin powder to form an insulating layer. The resin powder contains fluororesin and particles (A) with a particle size of 10 μm or more and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer. Step 2: A conductive layer is laminated on at least one surface in the thickness direction of the aforementioned insulating layer via an adhesive layer.

(Step 1) In Step 1, a resin powder containing particles (A) and not containing particles having a particle size exceeding the total thickness of the insulating layer and the adhesive layer is used. The average particle size of the resin powder used in step 1 is preferably 0.3-25 μm, preferably 0.5-20 μm, more preferably 1-17 μm, and particularly preferably 2-15 μm. If the average particle size of the resin powder is more than the lower limit of the aforementioned range, the resin powder has sufficient fluidity and is easy to handle. If the average particle size of the resin powder is less than the upper limit of the aforementioned range, the dispersibility of the resin powder in the liquid medium is good. The smaller the average particle size of the resin powder, the better the filling rate of the resin powder to the insulating layer, and the better the electrical properties (low dielectric constant, etc.) of the insulating layer. And can easily thin the printed substrate.

When using resin powder containing particles (A) and particles (B), it is advisable to use powder with a peak particle size of 10-100μm (hereinafter also referred to as "powder (a)") and a powder with a peak particle size of 0.3-8μm (below Also called "powder (b)") mixed resin powder. In this case, the polymer (X) is preferably used to form at least one of the powder (a) and the powder (b), and the polymer (X) is preferably used to form both the powder (a) and the powder (b).

The peak particle size of the powder (a) is 10-100 μm, preferably 11-50 μm, and more preferably 12-20 μm. The average particle size of the powder (a) is preferably 5 to 30 μm, and 6 to 25 μm is preferred, 7 to 23 μm is more preferred, and 8 to 20 μm is particularly preferred. The volume-based cumulative 90% diameter (D90) of the powder (a) is preferably 45 μm or less, preferably 35 μm or less, and particularly preferably 25 μm or less. If the D90 of the powder (a) is below the upper limit, the dispersibility to the liquid medium is better.

The bulk density of powder (a) is preferably above 0.05g/mL, and 0.05~0.5g/mL is preferred, and 0.08~0.5g/mL is particularly preferred. The dense packing density of powder (a) is preferably above 0.05g/mL, and 0.05~0.8g/mL is preferred, and 0.1~0.8g/mL is particularly preferred. The higher the density of the loose packing body or the dense packing body, the better the rationality of the powder (a). And it can increase the filling rate of the powder (a) to the insulating layer. If the density of the loose packing body or the tight packing body density is below the upper limit of the aforementioned range, it can be used in a general manufacturing process.

The peak particle size of powder (b) is 0.3-8μm, preferably 0.4-6μm, preferably 0.5-5μm. The average particle size of the powder (b) is preferably 0.3-6 μm, preferably 0.3-5 μm, more preferably 0.3-4 μm, particularly preferably 0.3-3 μm. The volume-based cumulative 90% diameter length (D90) of the powder (b) is preferably 8 μm or less, preferably 7 μm or less, and particularly preferably 6 μm or less. If the D90 of the powder (b) is below the upper limit, the dispersibility to the liquid medium is better.

The bulk density of powder (b) is preferably above 0.05g/mL, and 0.05~0.5g/mL is preferred, and 0.08~0.5g/mL is particularly preferred. The dense packing density of powder (b) is preferably above 0.05g/mL, and 0.05~0.8g/mL is preferred, and 0.1~0.8g/mL is particularly preferred.

In step 1, it is preferable to use a dispersion in which resin powder has been dispersed in a liquid medium to form an insulating layer. Specifically, it is advisable to mix a dispersion containing resin powder and a liquid containing the resin (hereinafter also referred to as "material resin") or its raw materials (hereinafter also referred to as "resin liquid") used to form the insulating layer film to form a liquid composition After finishing, the liquid composition is used to form an insulating layer. Compared with the case where the resin powder is mixed with the resin liquid in a powder state, mixing the dispersion liquid with the resin liquid does not cause the resin powder to scatter, and can be uniformly dispersed in the material resin or its raw materials. In addition, in the manufacturing method of the present invention, the resin powder may be mixed in a powder state with the resin liquid to form a liquid composition, or the material resin and the dispersion liquid may be mixed to form a liquid composition.

The mixing method of the dispersion liquid and the resin liquid is not particularly limited, and a method using a known stirrer can be mentioned. When it is desired to make the liquid composition contain fillers, hardeners, etc., these can be added to the dispersion before mixing, or can be added to the resin solution before mixing, or can be added to the mixed solution after mixing.

烷等醚類；乳酸乙酯、乙酸乙酯等酯類；甲基乙基酮、甲基異丙基酮等酮類；乙二醇單異丙基醚等甘醇醚類；甲賽璐蘇、乙賽璐蘇等賽璐蘇類；乙苯、甲苯、二甲苯等芳香族化合物等。液態介質可單獨使用1種亦可將2種以上併用。 另，液態介質中不含用於形成絕緣層之薄膜的樹脂或其原料中之液狀成分。且液態介質為不與聚合物(X)反應之化合物。The liquid medium used for the dispersion can be a well-known liquid medium, for example: water; alcohols such as methanol and ethanol; N,N-dimethylformamide, N,N-dimethylacetamide, N- Nitrogen-containing compounds such as methyl-2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide; diethyl ether, two

Ethers such as alkane; 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 cellulose , Cellulose, such as celluloid; Aromatic compounds such as ethylbenzene, toluene, xylene, etc. The liquid medium may be used alone or in combination of two or more kinds. In addition, the liquid medium does not contain liquid components in the resin or its raw materials used to form the insulating layer. And the liquid medium is a compound that does not react with the polymer (X).

Relative to 100 parts by mass of the resin powder, the content of the liquid medium in the dispersion is preferably 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, and particularly preferably 30 to 250 parts by mass. If the content of the liquid medium is within the aforementioned range, the coating property during film formation is good. In addition, if the content of the liquid medium is below the upper limit of the aforementioned range, since the amount of the liquid medium used is small, it is not easy to cause poor appearance of the film product due to the process of removing the liquid medium.

The dispersion may also contain a surfactant. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, and cationic surfactants. Among them, the surfactant is preferably a nonionic surfactant. A surfactant may be used individually by 1 type, and may use 2 or more types together.

When the dispersion contains a surfactant, relative to 100 parts by mass of the resin powder, the content of the surfactant in the dispersion is preferably 0.1-20 parts by mass, preferably 0.2-10 parts by mass, and particularly preferably 0.3-7 parts by mass. If the content of the surfactant is more than the lower limit of the aforementioned range, excellent dispersibility can be easily obtained. If the surfactant content is below the upper limit of the aforementioned range, the characteristics of the resin powder can be obtained without being affected by the characteristics of the surfactant.

The manufacturing method of the dispersion is not particularly limited, and it can be, for example, a method of mixing and stirring resin powder, surfactants, fillers, and liquid medium used as needed.

The material resin used for the resin liquid is the resin mentioned in the description of the insulating layer. The raw material of the material resin can be, for example, an aromatic polyimide precursor (polyamide acid), and a fully aromatic polyimide prepared by condensation polymerization of aromatic polycarboxylic dianhydrides and aromatic diamines. Displacement (polyamide acid) is suitable. Specific examples of aromatic polycarboxylic dianhydrides and aromatic diamines include those described in paragraphs [0055] and [0057] of JP 2012-145676 A, etc. These may be used individually by 1 type, and may use 2 or more types together.

The raw material of the material resin can also use the raw material precursor of TPI, that is, polyamide acid prepared by polycondensation of polycarboxylic dianhydride or its derivatives and diamine. Examples of polycarboxylic dianhydrides or their derivatives and diamines of polyamide acid that can form TPI raw materials include those described in paragraphs [0019] and [0020] of Japanese Patent No. 5766125.

The resin liquid can be used as it is when the material resin or its raw materials are in liquid form. When the material resin or its raw material is in a non-liquid state, it may be dissolved or dispersed in a liquid medium to make a resin liquid. The liquid medium in which the material resin or its raw material can be dissolved or dispersed is not particularly limited. For example, from the list of liquid media that can be used as a dispersion liquid, it can be appropriately selected according to the type of the material resin or its raw material.

When a thermosetting resin or its raw material is used for the resin liquid, the liquid composition may also contain a curing agent. Examples of hardeners include thermal hardeners (melamine resin, urethane resin, etc.), epoxy hardeners (phenolic phenol resin, dihydrazine isophthalate, dihydrazine adipate, etc.).

The content of the liquid medium in the liquid composition is preferably 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, and particularly preferably 30 to 250 parts by mass, relative to the total of 100 parts by mass of the resin powder and raw resin or its raw materials. If the content of the liquid medium is above the lower limit of the aforementioned range, the viscosity of the liquid composition will not be too high, and the coating properties during film formation will be good. If the content of the liquid medium is below the upper limit of the aforementioned range, the viscosity of the liquid composition will not be too low, the coating performance during film formation is good, and the amount of liquid medium used is small, so it is not easy to cause film formation due to the process of removing the liquid medium The appearance of the product is poor. In addition, when the resin liquid already contains a liquid medium, the content of the liquid medium in the liquid composition means the total content of the liquid medium of the dispersion liquid and the liquid medium of the resin liquid.

When the liquid composition contains a hardener, the content of the hardener in the liquid composition is preferably 0.5 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents relative to the amount of reactive groups possessed by the thermosetting resin or its raw materials.

Regarding the method of forming an insulating layer using a liquid composition, when forming an insulating layer with a thin film, for example, a method of forming a film using a liquid composition and then heating it after drying to obtain a thin film. The method for forming the film of the liquid composition is not particularly limited. Examples include spray coating, roll coating, spin coating, bar coating and other well-known wet coating methods to coat the liquid composition on a flat surface. method.

After forming the film of the liquid composition, at least a part of the liquid medium is removed by drying. When drying, it is not necessary to completely remove the liquid medium, as long as the coating film after film formation can stably maintain the film shape. When drying, it is preferable to remove more than 50% by mass of the liquid medium contained in the liquid composition.

The method of drying the coating film after film formation is not particularly limited, and examples include a heating method using an oven, a heating method using a continuous drying furnace, and the like. The drying temperature should be within the range that does not generate bubbles when removing the liquid medium, for example, 50~250°C, preferably 70~220°C. The drying time is preferably 0.1 to 30 minutes, preferably 0.5 to 20 minutes. Drying can be carried out in one stage, or in two or more stages at different temperatures.

When the raw material of the thermoplastic resin is used in the resin liquid, the raw material of the thermoplastic resin will be made into a thermoplastic resin by heating after drying. For example, when using polyamide which is a raw material of TPI, heat is used to imidize polyamide after drying to make TPI. At this time, the heating temperature after drying can be set at 350~550°C, for example.

When a thermosetting resin is used in the resin liquid, the thermosetting resin is cured by heating after drying. In addition, when using the raw material of thermosetting resin (polyamide acid of the precursor of aromatic polyimide, etc.), after drying, the thermosetting resin raw material is made into thermosetting resin by heating. hardening. The heating temperature after drying can be set appropriately according to the type of thermosetting resin, for example, it can be set at 50~250℃ when using epoxy resin. Drying and subsequent heating can also be continued.

When forming an insulating layer with a fiber-reinforced film, for example, a method of infiltrating a reinforcing fiber base material with a liquid composition and then heating it after drying to obtain a fiber-reinforced film. Specifically, after the liquid composition is infiltrated into the reinforcing fiber base material, it is dried to remove at least a part of the liquid medium and then heated. The drying and heating after the infiltration can be performed in the same manner as the drying and heating in the aforementioned film manufacturing method.

In addition, the liquid composition may be impregnated into the reinforcing fiber base material and dried to form a prepreg. When manufacturing a prepreg, the method of infiltrating the reinforcing fiber base material with the liquid composition can be performed in the same manner as the method of manufacturing a fiber-reinforced film. The drying after soaking can be performed in the same way as the drying in the film manufacturing method. Liquid media may also remain in the prepreg. In the prepreg, it is preferable that more than 70% by mass of the liquid medium contained in the liquid composition has been removed. In the case of a prepreg, when a thermosetting resin or a liquid composition containing a thermosetting resin raw material is used, the curable resin may be in a semi-cured state after drying.

In addition, the prepreg, in addition to printed circuit boards, can also be used as sheet pile materials that require durability and light weight in embankment construction, or used to manufacture airplanes, automobiles, ships, windmills, sports equipment and other guiding components for various purposes. The materials used.

(Step 2) A method of laminating a conductive layer on one side or both sides of the insulating layer with adhesive interposed therebetween can be, for example, a method of laminating the insulating layer and the metal foil by thermal lamination using a material for forming the adhesive layer such as TPI. The following method can also be used: After dispersing or dissolving the liquid that forms the adhesive layer such as TPI, apply it on the surface of the insulating layer and the surface of the metal foil respectively, or apply it on only one surface and dry it, These are laminated with the coating films facing each other and then hot pressed.

[Method of manufacturing printed circuit board] The method of manufacturing a printed circuit board of the present invention is a method of obtaining a printed circuit board by etching the conductive layer of the metal laminate of the present invention to form a pattern circuit. In this way, a printed circuit board can be manufactured by using the metal laminate of the present invention. The etching of the metal layer can be performed by a known method.

In the manufacturing method of the printed circuit board of the present invention, after etching the metal layer to form a patterned circuit, an interlayer insulating film is formed on the patterned circuit, and then a patterned circuit is further formed on the interlayer insulating film. The interlayer insulating film can be formed using, for example, the liquid composition produced by the production method of the present invention. Specifically, the following methods can be cited. After the conductive layer of the metal laminate is etched to form a patterned circuit, the aforementioned liquid composition is coated on the patterned circuit, and after drying, it is heated to form an interlayer insulating film. Next, a conductive layer is formed on the aforementioned interlayer insulating film by vapor deposition or the like, and etching is performed to further form a pattern circuit.

When manufacturing a printed circuit board, a solder resist layer can also be laminated on the patterned circuit. The solder mask can be formed of the aforementioned liquid composition, for example. Specifically, the liquid composition of the present invention can also be coated on a patterned circuit and heated after drying to form a solder resist layer.

Moreover, when manufacturing a printed circuit board, a cover film may be laminated|stacked. The coating film is typically composed of a base film and an adhesive layer formed on the surface thereof, and the surface of the adhesive layer is bonded to the printed substrate. As the base film of the cover film, for example, the aforementioned films can be used. In addition, it is also possible to form an interlayer insulating film using the aforementioned thin film on a patterned circuit formed by etching the conductive layer of the metal laminate, and laminate a polyimide film as a cover film.

The printed circuit board produced by the above-mentioned manufacturing method of the present invention can be effectively used as a board for electronic equipment such as radars, Internet routers, backplanes, and wireless base stations that require high-frequency characteristics, or as a board for various sensors for automobiles, and engine management sensors. The substrate for the sensor is particularly suitable for applications aimed at reducing the transmission loss in the millimeter wave band. Example

Hereinafter, the present invention will be specifically explained with examples, but the present invention is not limited by the following description. Examples 1 to 4, 8, and 9 are examples, and examples 5 to 7, and 10 are comparative examples. [Measurement method] The various measurement methods for the fluorinated copolymer and resin powder are shown below. (1) Copolymerization composition In the copolymerization composition of the fluorinated copolymer, the content ratio (mol %) of the unit mainly composed of NAH is determined by the following infrared absorption spectrum analysis. The content ratios of other units are calculated by melting NMR analysis and fluorine content analysis.

<The content ratio of NAH-based units (mol %)> After the fluorinated copolymer is press-formed to obtain a 200 μm thick film, it is analyzed by infrared spectroscopy to obtain an infrared absorption spectrum. In the infrared absorption spectrum, the absorption peak of the NAH-based unit in the fluorinated copolymer appears at 1778 cm ^-1 . Measure the absorbance of the absorption peak, and use the molar absorption coefficient of NAH 20810mol ^-1 ·l·cm ^-1 to determine the content ratio of the NAH-based unit in the fluorinated copolymer.

(2) Melting point (°C) Use a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC device) to record the melting peak of the fluorinated copolymer at a rate of 10°C/min. ) As the melting point (Tm).

(3) MFR (g/10 minutes) Using a melt index tester (manufactured by Technol Seven Co., Ltd.), measure the flow rate from a nozzle with a diameter of 2 mm and a length of 8 mm at 372°C and a load of 49 N for 10 minutes (unit time) The mass (g) of the fluorinated copolymer is regarded as MFR.

(4) The relative permittivity is measured by SPDR (Split-Post Dielectric Resonator) method at a frequency of 2.5GHz in an environment within the range of 23℃±2℃ and 50±5%RH. The obtained value is used as the relative permittivity.

(5) The average particle size of the fluorine-containing copolymer overlaps in order from the top with 2.000 mesh screen (pore size 2.400mm), 1.410 mesh screen (pore size 1.705mm), 1.000 mesh screen (pore size 1.205mm), 0.710 mesh screen (pore size 0.855mm) ), 0.500 mesh screen (pore size 0.605mm), 0.250 mesh screen (pore size 0.375mm), 0.149 mesh screen (pore size 0.100mm) and receiving tray. Put the sample (fluorine-containing copolymer) from above and sieving with a shaker for 30 minutes. After that, measure the mass of the sample remaining on each sieve, and list the total passing mass corresponding to each pore size value in the graph, and use the particle size when the total passing mass reaches 50% as the average particle size of the sample.

(6) Measure the peak particle size, average particle size (D50) and D90 of the resin powder. Use a laser diffraction scattering particle size distribution measuring device (manufactured by Horiba Manufacturing Co., Ltd., LA-920 measuring device) to measure the resin powder after dispersing in water Particle size distribution, calculate the peak particle size, average particle size (D50) and D90.

(7) Bulk density and tight packing density The loose packing density and tight packing density of the resin powder are measured by the method described in paragraphs [0117] and [0118] of International Publication No. 2016/017801.

(8) Peel strength A test piece with a length of 100 mm and a width of 10 mm was cut out from the metal laminates obtained in each example. Peel off between the adhesive layer and the insulating layer to a position that is 50 mm away from one end in the length direction of the test piece. Next, using a tensile testing machine (manufactured by Orientec Co., LTD) with a position 50mm away from one end in the longitudinal direction of the test piece as the center, peeling 90 degrees at a tensile speed of 50mm/min and using the maximum load as the peel strength (N/10mm). The greater the peel strength, the better the adhesion between the insulating layer and the adhesive layer.

(9) The particle size of the particles and aggregates in the insulator layer was measured using a scanning electron microscope (manufactured by Hitachi High-Technologies Co., model name: S-4800), and the diameter of 100 powder particles was measured at a magnification of 5000 times. The diameter is taken as the particle size. The particle diameter is measured by measuring the long side as the diameter. When the powder is coagulated, the agglomerate is used as a particle to measure the diameter.

(10) A method for measuring the volume occupied by particles and aggregates in the insulating layer in the insulating layer. The volume occupied by the particles and aggregates in the insulating layer in the insulating layer is to first obtain the average particle size of 100 particles and aggregates obtained by the aforementioned method, and the randomly selected 300μm square range has a particle size of 10μm or more After calculating the total number of particles and the average particle size of particles above 10μm, calculate the area ratio of the particles in the insulating layer. The area ratio was calculated as the volume ratio. In addition, the areas of particles and aggregates are assumed to be true circles, and the area is calculated from the diameter and number.

[Manufacturing Example 1] NAH (Nadic anhydride, manufactured by Hitachi Chemical Co., Ltd.) and PPVE (CF ₂ =CFO(CF ₂ ) ₃ F, manufactured by Asahi Glass Co., Ltd.) are used together as monomers forming unit (1), according to International Publication The procedure described in paragraph [0123] of No. 2016/017801 was used to produce copolymer (X-1). The copolymerization composition of the copolymer (X-1) is NAH unit/TFE unit/PPVE unit=0.1/97.9/2.0 (mol%). The melting point of the copolymer (X1-1) is 300°C, the relative dielectric constant is 2.1, the MFR is 17.6 g/10 minutes, and the average particle size is 1554 μm.

Next, a jet mill (manufactured by SEISHIN ENTERPRISE Co., Ltd., monorail jet mill FS-4 model) was used to pulverize the copolymer (X-1) under the conditions of a pulverizing pressure of 0.5 MPa and a processing speed of 1 kg/hr to obtain a resin After the powder, the resin powder was classified using a high-efficiency precision air classifier under the condition of a throughput of 0.8 kg/hr to obtain a powder (a-1). The peak particle diameter of the powder (a-1) was 17 μm, the average particle diameter was 12 μm, and the D90 was 19 μm. The bulk density of the powder (a-1) is 0.280g/mL, and the density of the compact packing is 0.323g/mL. The powder (a-1) does not contain particles with a particle size exceeding 36 μm.

[Manufacturing Example 2] Using the same high-efficiency precision air classifier as in Manufacturing Example 1, the powder (a-1) was classified under the condition of a throughput of 0.5 kg/hr to obtain a powder (b-1). The peak particle diameter of the powder (b-1) was 2.2 μm, the average particle diameter was 2.1 μm, and the D90 was 7.1 μm. The bulk density of powder (b-1) is 0.278g/mL, and the density of tight packing is 0.328g/mL.

[Manufacturing Example 3] Using the same high-efficiency precision air classifier as in Manufacturing Example 1, the powder (a-1) was classified under the condition of a throughput of 0.5 kg/hr to obtain a powder (b-2). The peak particle diameter of the powder (b-2) was 1.8 μm, the average particle diameter was 1.7 μm, and the D90 was 6.5 μm. The bulk density of powder (b-2) is 0.270g/mL, and the density of tight packing is 0.321g/mL.

[Manufacturing Example 4] Using the same high-efficiency precision air classifier as in Manufacturing Example 1, the resin powder composed of PTFE (L150J manufactured by Asahi Glass Co., Ltd.) was classified under the condition of a throughput of 0.3 kg/hr to obtain a powder (b- 3). The peak particle diameter of the powder (b-3) was 1.8 μm, the average particle diameter was 1.6 μm, and the D90 was 6.3 μm. The bulk density of powder (b-3) was 0.271g/mL, and the density of tight packing was 0.318g/mL.

[Manufacturing Example 5] A high-efficiency precision air classifier (manufactured by SEISHIN ENTERPRISE Co., Ltd., Classiel N-01 type) was used to classify the powder (a-1) under the condition of a throughput of 0.7 kg/hr. Powder (b-4). The peak particle diameter of the powder (b-4) was 3.5 μm, the average particle diameter was 4.8 μm, and the D90 was 9.7 μm. The bulk density of powder (b-4) was 0.284g/mL, and the density of tight packing was 0.333g/mL. Relative to the total volume of the powder (b-4), the ratio of particles (A) with a particle diameter of 10 μm or more is 7 vol%, and the ratio of particles (B) with a particle diameter of less than 10 μm is 93 vol%.

A resin powder (L150J manufactured by Asahi Glass Co., Ltd.) composed of PTFE was prepared as the powder (a-2). The peak particle diameter of the powder (a-2) was 12 μm, the average particle diameter was 12 μm, and the D90 was 27 μm. The powder (a-2) does not contain particles with a particle size exceeding 36 μm.

Prepare resin powder (L170JE manufactured by Asahi Glass Co., Ltd.) composed of PTFE as powder (b-5). The peak particle diameter of the powder (b-5) was 0.3 μm, the average particle diameter was 0.3 μm, and the D90 was 0.4 μm.

[Example 1] A predetermined amount of powder was fed into a 1L container, and the powder (a-1) and the powder (b-1) were mixed by manual shaking for 10 minutes. With respect to the total volume of the obtained resin powder (mixed powder), the ratio of particles (A) with a particle diameter of 10 μm or more is 18% by volume, and the ratio of particles (B) with a particle diameter of less than 10 μm is 82% by volume. The above-mentioned mixed powder is added to the resin liquid U-varnish (manufactured by Ube Industries). The addition amount is fed in such a way that the weight ratio of the solid content in the U-varnish to the mass of the mixed powder is 59:41. Stir for 1 hour with a stirrer at 1000 rpm. After 30 minutes of vacuum degassing treatment, a liquid composition was obtained. In the liquid composition, no resin powder agglomerated in appearance. On the surface of electrolytic copper foil (made by Futian Metal Foil Powder Co., Ltd., CF-T4X-SVR-12, thickness: 12μm, surface roughness (Rz): 1.2μm), the thickness of the coating film (insulating layer) after drying is taken as The liquid composition filtered by the filter is coated in a 24μm way. It was heated in an oven at 170°C for 5 minutes, at 190°C for 3 minutes, and heated at 220°C for 1 minute for drying to form an insulating layer to obtain a single-sided copper-clad laminate. Then, the copper foil is removed by etching to obtain a powder-containing film.

After adding 115.6g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) to 780g of N,N-dimethylformamide (DMF) cooled to 10°C, Then slowly add 78.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). Next, 3.8 g of ethylene bis(trimellitic acid monoester acid anhydride (TMEG)) was added, and after uniformly stirring for 30 minutes under an ice bath, a prepolymer was obtained. In the prepolymer solution, p-phenylenediamine (PDA ) After 25.2g, dissolve 46.4g of pyromellitic dianhydride (PMDA), and carefully add 115.1g (PMDA: 0.038mol) of a 7.2% by mass DMF solution of PMDA prepared separately, and stop adding until the viscosity reaches about 2500 poise . Next, stir for 1 hour to obtain a polyamide acid solution with a rotational viscosity of 2600 poise at 23°C. On electrolytic copper foil (manufactured by Futian Metal Foil Co., Ltd., CF-T4X-SVR-12, thickness: 12μm, rough surface Degree (Rz): 1.2μm) on the surface of the coating film (adhesive layer) after drying the thickness of 12μm coated the above-mentioned amic acid solution filtered through the filter. Heated in an oven at 150 ℃ for 5 minutes, Heat at 180°C for 5 minutes and at 250°C for 5 minutes to dry to form an adhesive layer to obtain a single-sided copper-clad laminate. Laminate the powder-containing film on both sides with copper foil (conductive layer) facing the outside After the aforementioned single-sided copper-clad laminate, under the conditions of a pressing temperature of 350°C, a pressing pressure of 4.0 MPa, and a pressing time of 15 minutes, vacuum hot pressing is performed to imidize them, and a copper/thermoplastic polyimide layer is obtained. (Adhesive layer)/non-thermoplastic polyimide layer (insulating layer)/thermoplastic polyimide layer (adhesive layer)/copper double-sided copper-clad laminate.

[Examples 2 to 7] Except that the resin powder used was replaced as shown in Table 1, a metal laminate was produced in the same manner as in Example 1.

[Examples 8, 9] The metal was prepared in the same manner as in Example 1, except that the addition amount of the mixed powder was changed to feed it so that the weight of the solid content in the U-varnish and the mass ratio of the mixed powder were 85:15. Laminated board. [Example 10] Add the powder (a-2): powder (b-2) to the mixed powder of 75% by volume: 25% by volume so that the weight ratio of the solid content in the U-varnish to the mass ratio of the mixed powder becomes 38:62 Except for this change, a metal laminate was produced in the same manner as in Example 1.

The conditions and evaluation results of each case are listed in Table 1.

[Table 1]

As shown in Table 1, Examples 1 to 4, 8, and 9 use resin powder that contains particles (A) and does not contain particles exceeding the total thickness of the insulating layer and the adhesive layer, and the surface of the insulating layer on the adhesive layer side is coarse The degree is set to 0.5~3.0μm, so the peeling strength of the insulating layer and the adhesive layer is high, and a high degree of adhesive strength is obtained between the insulating layer and the adhesive layer. On the other hand, in Examples 5-7, the peeling strength of the insulating layer and the adhesive layer is lower than that of the examples, and the adhesive strength between the insulating layer and the adhesive layer is poor. In addition, in Example 10 where the surface roughness of the insulating layer is 4.2μm, which is more than 3.0μm, when the peeling strength between the adhesive layer and the insulating layer is measured, the adhesive strength between the copper foil and the adhesive layer is 3N/cm, which is quite low, and the peeling interface is Between the layer and the copper foil, it is impossible to measure the peel strength of the insulating layer and the adhesive layer. From the viewpoint of weak peeling strength of copper clad laminates, it is not suitable as a copper clad laminate for printed circuit boards. In addition, the particles (A) contained in the insulating layers of Examples 5-7 and 10 and aggregates with a particle size of 10 μm or more contained less than 5-18% by volume, and both had low peel strength as mentioned above and were not suitable for copper-clad laminates. In addition, the entire contents of the specification, patent application scope, drawings, and abstract of Japanese Patent Application No. 2016-170803 filed on September 1, 2016 are cited here and incorporated as the disclosure of the specification of the present invention.

1, 2‧‧‧Metal laminate 10,20‧‧‧Insulation layer 10a, 20a, 20b‧‧‧Surface 12‧‧‧Adhesive layer 14‧‧‧Conductive layer 16, 30‧‧‧Resin powder 16a, 30a‧ ‧‧Particles (A) 16b, 30b‧‧‧Particles (B) 22‧‧‧The first subsequent layer 24‧‧‧The first conductive layer 26‧‧‧The second subsequent layer 28‧‧‧The second conductive layer d1~ d5‧‧‧Thickness

Fig. 1 is a schematic cross-sectional view showing an example of the metal laminate of the present invention. Fig. 2 is a schematic cross-sectional view showing another example of the metal laminate of the present invention.

1‧‧‧Metal Laminated Board

10‧‧‧Insulation layer

10a‧‧‧surface

12‧‧‧Next layer

14‧‧‧Conductive layer

16‧‧‧Resin powder

16a‧‧‧Particle (A)

16b‧‧‧Particle (B)

d1, d2‧‧‧thickness

Claims (19)

A metal laminated board comprising: an insulating layer; an adhesive layer provided on at least one surface in the thickness direction of the insulating layer; and a conductive layer provided on the surface of the adhesive layer opposite to the insulating layer Wherein, the insulating layer contains a fluorine-containing resin resin powder, the resin powder contains particles with a particle size of 10 μm or more and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer, and the particle size in the insulating layer The content of particles above 10μm is 5-18% by volume, the thickness of the aforementioned insulating layer is 6-300μm, and the surface roughness of the aforementioned insulating layer provided with the aforementioned adhesive layer is 0.5-3.0μm. The metal laminate of claim 1, wherein the aforementioned resin powder further contains particles with a particle diameter of less than 10 μm, and relative to the total volume (100% by volume) of particles with a particle diameter of 10 μm or more and particles with a particle diameter of less than 10 μm, the aforementioned particles The content of particles with a diameter of 10μm or more is 8~63% by volume, and the content of particles with a diameter of less than 10μm is 37~92% by volume. The metal laminate of claim 1 or 2, wherein the aforementioned fluororesin is a fluorine-containing copolymer, which has a unit with the following functional groups and a unit based on tetrafluoroethylene, and has a melting point of 260-320°C, and the aforementioned functional group It is selected from the group consisting of carbonyl group, hydroxyl group, epoxy group and isocyanate group At least one functional group in the group. The metal laminate of claim 3, wherein the aforementioned fluorine-containing copolymer has a unit with the aforementioned functional group, a unit mainly composed of tetrafluoroethylene, and a unit mainly composed of perfluoro(alkyl vinyl ether), and is relative to The total amount of all units, each unit has the following ratio; the unit with the aforementioned functional group: 0.01~3 mol%; the unit with tetrafluoroethylene as the main body: 90~99.89 mol%; Base ether) as the main unit: 0.1~9.99 mol%. Such as the metal laminate of claim 3, wherein the aforementioned fluorinated copolymer has a unit having the aforementioned functional group, a unit mainly composed of tetrafluoroethylene, and a unit mainly composed of hexafluoropropylene, and relative to the total amount of all the units, Each unit has the following ratio; the unit with the aforementioned functional group: 0.01~3 mol%; the unit with tetrafluoroethylene as the main body: 90~99.89 mol%; the aforementioned unit with hexafluoropropylene as the main body: 0.1~9.99 Mol%. The metal laminate of claim 3, wherein the aforementioned functional group is a carbonyl group-containing group, and the aforementioned carbonyl group-containing group is selected from the group consisting of a hydrocarbon group having a carbonyl group between carbon atoms, a carbonate group, a carboxyl group, At least one of the group consisting of haloformyl, alkoxycarbonyl and acid anhydride residues. Such as the metal laminate of claim 1 or 2, wherein the relative dielectric constants of the aforementioned insulating layer and the aforementioned adhesive layer are both 2.1~3.5. The metal laminate of claim 1 or 2, wherein the aforementioned insulating layer further contains polyimide. The metal laminate of claim 1 or 2, wherein the thickness of the insulating layer is 7-50μm, the resin powder is a mixed powder containing polytetrafluoroethylene and a fluorinated copolymer, and the fluorinated copolymer has the following The functional group unit and the unit mainly composed of tetrafluoroethylene, the aforementioned functional group is selected from at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, and an isocyanate group. A method of manufacturing a metal laminated board is a method of manufacturing a metal laminated board as claimed in any one of claims 1 to 9, the method of manufacturing uses resin powder to form the insulating layer, and then the thickness of the insulating layer is interposed by the adhesive layer A conductive layer is laminated on at least one surface in the direction; wherein the resin powder contains fluororesin and contains particles with a particle size of 10 μm or more, and does not contain particles with a particle size exceeding the total thickness of the insulating layer and the adhesive layer. For example, the method for manufacturing a metal laminate of claim 10 uses resin powder mixed with the following powders: powder (a) with a peak particle diameter of 10-100 μm; and powder (b) with a peak particle diameter of 0.3-8 μm. The method for manufacturing a metal laminate according to claim 10 or 11, wherein at least one of the aforementioned powder (a) and the aforementioned powder (b) is a fluorinated copolymer, and the fluorinated copolymer has a unit having the following functional group With a unit with tetrafluoroethylene as the main body and a melting point of 260~320℃, the aforementioned functional group is selected from at least one functional group selected from the group consisting of carbonyl-containing groups, hydroxyl groups, epoxy groups and isocyanate groups . Such as claim 10 or 11 of the method of manufacturing a metal laminate, which uses a dispersion in which the aforementioned resin powder has been dispersed in a liquid medium To form the aforementioned insulating layer. A method for manufacturing a printed circuit board is obtained by etching the aforementioned conductive layer of a metal laminated board according to any one of claims 1 to 9 to form a pattern circuit. An insulating layer containing a fluorine-containing resin resin powder. The resin powder in the insulating layer contains at least one of particles with a particle size of 10 μm or more and agglomerates with a particle size of 10 μm or more, relative to the total volume of the material forming the insulating layer The content of the aforementioned particles and agglomerates is 5-18% by volume, and the aforementioned resin powder further contains particles with a particle size of less than 10μm, and relative to particles with a particle size of 10μm or more, and agglomerates with a particle size of 10μm or more. The total volume of particles of 10μm (100% by volume), the content of particles with a particle size of 10μm or more and agglomerates with a particle size of 10μm or more is 8~63% by volume, and the content of particles with a particle size of less than 10μm is 37~92% by volume; The thickness of the aforementioned insulating layer is 6 to 300 μm. The insulating layer of claim 15, wherein the aforementioned fluororesin is a fluorine-containing copolymer, which has a unit with the following functional groups and a unit based on tetrafluoroethylene, and has a melting point of 260-320°C, and the aforementioned functional groups are selected from At least one functional group in the group consisting of a carbonyl-containing group, a hydroxyl group, an epoxy group, and an isocyanate group. For example, the insulating layer of claim 15 or 16, its relative dielectric constant is 2.1~3.5. A method of manufacturing an insulating layer is a method of manufacturing an insulating layer as claimed in any one of claims 15 to 17, the manufacturing method using a dispersion in which resin powder has been dispersed in a liquid medium to form the aforementioned insulating layer, The resin powder is mixed with the following powders: powder (a) with a peak particle diameter of 10 to 100 μm; and powder (b) with a peak particle diameter of 0.3 to 8 μm. A metal laminated board comprising: an insulating layer; an adhesive layer provided on at least one surface in the thickness direction of the insulating layer; and a conductive layer provided on the surface of the adhesive layer opposite to the insulating layer; wherein The aforementioned insulating layer is the insulating layer according to any one of claims 15 to 17, and does not contain particles with a particle size exceeding the total thickness of the aforementioned insulating layer and the aforementioned adhesive layer and aggregates with a particle size of 10 μm or more.

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