TW202138200A - Method for producing multilayer body and liquid composition - Google Patents

Abstract

To provide: a multilayer body which has a polymer layer that is provided with the physical properties of a tetrafluoroethylene polymer and the physical properties of a maleimide compound; and a liquid composition which contains a tetrafluoroethylene polymer and a maleimide compound. A method for producing a multilayer body according to the present invention forms a polymer layer by: applying a liquid composition, which contains a powder of a tetrafluoroethylene polymer having a melting temperature of 260 DEG C or more and a thermosetting compound having a maleimide group and an arylene group, to the surface of a base material layer; heating the liquid composition at a temperature that is not less than 100 DEG C but less than the melting temperature of the tetrafluoroethylene polymer; and further heating the liquid composition at a temperature that is not less than the melting temperature of the tetrafluoroethylene polymer. A liquid composition according to the present invention contains a powder of a specific tetrafluoroethylene polymer and the above-described thermosetting compound.

Description

Manufacturing method of laminated body and liquid composition

The present invention relates to a method for manufacturing a laminate and a liquid composition.

For printed wiring boards used to transmit high-frequency signals, excellent transmission characteristics are required. As the insulating layer material of printed wiring boards with higher transmission characteristics, tetrafluoroethylene polymers with lower relative permittivity and dielectric loss factor have attracted much attention. As a material for forming an insulating layer containing a tetrafluoroethylene-based polymer, a dispersion liquid containing a tetrafluoroethylene-based polymer powder is known. Patent Document 1 describes a method for producing a copper foil with a polymer layer, in which a film containing a liquid composition containing polytetrafluoroethylene powder and a maleimide compound is attached to the surface of the copper foil. And heat it up. Prior art literature Patent literature

Patent Document 1: International Publication No. 2018/051715

[The problem to be solved by the invention]

However, the copper foil with a polymer layer of Patent Document 1 not only has the problem that the polymer layer (insulating layer) formed by the film of the liquid composition and the copper foil are easily peeled off, but also has the problem that it is easy to warp And the reliability of the printed wiring board obtained by processing it is also insufficient. The inventors conducted intensive research, and as a result, obtained the following insights: When using a liquid composition containing a tetrafluoroethylene polymer powder with a specific melting temperature and a specific maleimide compound, the specific difference When the polymer layer is formed by heating under temperature conditions, a copper foil with a polymer layer (laminated body) that is not easily peeled and not easily warped can be obtained, and a printed wiring board with excellent transmission characteristics can be obtained. In addition, the inventors of the present invention have also found that a liquid composition containing a specific powder and a specific maleimide compound has excellent dispersibility and excellent handling properties. The object of the present invention is to provide the laminate and the liquid composition. [Technical means to solve the problem]

The present invention has the following aspects. <1> A method for manufacturing a laminate, wherein the surface of the substrate layer is provided with a combination of tetrafluoroethylene polymer powder with a melting temperature of 260°C or higher, and a thermosetting compound having a maleimide group and an arylene group The liquid composition is heated at a temperature above 100°C and below the melting temperature of the above-mentioned tetrafluoroethylene-based polymer, and further heated at a temperature above the melting temperature of the above-mentioned tetrafluoroethylene-based polymer to form polymerization The object layer is obtained to obtain a laminate having the above-mentioned base layer and the above-mentioned polymer layer. <2> The manufacturing method of the above <1>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing perfluoro(alkyl vinyl ether)-based units or hexafluoropropylene-based units. <3> The manufacturing method as in the above <1> or <2>, wherein the above-mentioned tetrafluoroethylene-based polymer contains a unit based on perfluoro(alkyl vinyl ether) and a tetrafluoroethylene-based polymer with a polar functional group Or, the above-mentioned tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer that contains 2.0-5.0 mol% of perfluoro(alkyl vinyl ether)-based units relative to the total unit and does not have a polar functional group . <4> The production method according to any one of the above <1> to <3>, wherein the liquid composition further contains an inorganic filler. <5> The production method according to any one of the above <1> to <4>, wherein the liquid composition further contains an elastomer. <6> The production method according to any one of the above <1> to <5>, wherein the ratio of the content of the thermosetting compound in the liquid composition to the content of the tetrafluoroethylene-based polymer is 0.2 or less. <7> The production method according to any one of the above <1> to <6>, wherein the glass transition temperature of the cured product of the thermosetting compound is less than the melting temperature of the tetrafluoroethylene-based polymer. <8> The manufacturing method according to any one of the above <1> to <7>, wherein the substrate layer is a metal foil or a polymer film. <9> A liquid composition containing a tetrafluoroethylene polymer powder containing a unit based on perfluoro(alkyl vinyl ether), and a thermosetting compound having a maleimide group and an arylene group, and The tetrafluoroethylene-based polymer has a polar functional group, or contains 2.0 to 5.0 mol% of the unit based on the perfluoro(alkyl vinyl ether) with respect to the total unit and does not have a polar functional group. <10> The liquid composition according to the above <9>, wherein the molecular weight of the thermosetting compound is 300-2000. <11> The liquid composition according to the above <9> or <10>, wherein the average particle size of the tetrafluoroethylene polymer powder is 40 μm or less. <12> The liquid composition of any one of the above-mentioned <9> to <11>, which further contains an inorganic filler. <13> The liquid composition of any one of the above-mentioned <9> to <12>, which further contains an elastomer. <14> The liquid composition of any one of the above <9> to <13>, wherein the ratio of the content of the thermosetting compound in the liquid composition to the content of the tetrafluoroethylene polymer is 0.2 the following. <15> The liquid composition according to any one of the above <9> to <14>, wherein the viscosity of the liquid composition at 25°C is 100 to 5000 mPa·s. [Effects of Invention]

According to the present invention, it is possible to obtain a laminate having a base layer and a polymer layer and excellent in peel strength and electrical properties. The polymer layer includes a cured product of a tetrafluoroethylene-based polymer and a specific thermosetting compound. In addition, a liquid composition containing a specific tetrafluoroethylene polymer powder and a specific maleimide compound and having excellent dispersibility and handling properties can be obtained.

The following terms have the following meanings. "Average particle size (D50)" is the cumulative 50% diameter of the object (powder or filler) powder determined by the laser diffraction scattering method. That is, the particle size distribution of the object is measured by the laser diffraction scattering method, the total volume of the cluster of object particles is set to 100%, and the cumulative curve is obtained. The above-mentioned "average particle diameter (D50)" is based on the cumulative The particle size at the point where the cumulative volume reaches 50% on the curve. "D90" is the cumulative 90% diameter of the object measured in the same way. The "melting temperature (melting point)" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method. "Glass transition temperature (Tg)" is the value measured by analyzing the polymer, hardened product, or elastomer by the dynamic viscoelasticity measurement (DMA) method. "Viscosity" is a value obtained by measuring a liquid composition at 25°C and a rotation speed of 30 rpm using a B-type viscometer. Repeat the measurement 3 times and take the average of the 3 measurements. The so-called "thixotropy ratio" refers to the viscosity η _{1 of the liquid composition measured at a rotation speed of 30 rpm, and the viscosity η 2} , η ₁ of the liquid composition measured at a rotation speed of 60 rpm. The value calculated by dividing by η _{2 (η 1} /η ₂ ). The "unit" in the polymer can be an atomic group formed directly from a monomer, or an atomic group obtained by converting a part of the structure by processing the obtained polymer by a specific method. The monomer A-based unit contained in the polymer is also abbreviated as "monomer A unit".

The production method of the present invention (hereinafter, also referred to as "this method") is a method in which a tetrafluoroethylene-based polymer containing a melting temperature of 260°C or higher (hereinafter, also referred to as " F polymer") powder, and a liquid composition of a thermosetting compound having a maleimide group and an arylene group (hereinafter, also referred to as "maleimide compound"), at a temperature above 100°C and no Heat at a temperature that reaches the melting temperature of the F polymer (hereinafter, also referred to as "initial heating"), and then heat at a temperature above the melting temperature of the F polymer (hereinafter, also referred to as "post-heating") The polymer layer is formed to produce a laminate having a base layer and a polymer layer.

According to this method, the following laminates can be obtained, which possess the physical properties of F polymer (electrical properties, etc.) and the physical properties of maleimide compounds (adhesiveness, low linear expansion, etc.), peel strength, and electrical properties to a high degree. Excellent properties and not easy to warp. Although the reason is not necessarily clear, the inventors of the present invention consider it as follows. If a liquid composition containing a maleimide compound with a higher polarity and a F polymer powder with a lower polarity is given to the base layer, and the polymer layer is formed by one heating, then the polymer layer , The hardened products of F polymer and maleimide-based compound are respectively localized. Therefore, the peel strength of the obtained laminate is reduced due to the linear expansion of the localized F polymer, which is easy to warp, and the electrical properties are easily affected by the localized maleimide compound. The hardened material is reduced.

In this way, in this method, the maleimide compound is partially hardened (reacted) by initial heating to reduce its polarity, and then the fine particles of the F polymer powder are melted and fired by the latter heating to form a polymer layer. . That is, in the later heating, the polymer layer is formed while the F polymer and the cured product of the maleimide-based compound are highly compatible with each other. As a result, a polymer layer in which the cured product of the F polymer and the maleimide compound is uniformly distributed is formed. Therefore, according to this method, it is possible to obtain a polymer layer with a high degree of physical properties (electrical properties of F polymer, adhesion of hardened maleimide compounds, low linear expansion, etc.) Layered body. In addition, in the polymer layer of the laminate, the cured product of the maleimide compound is dispersed in the flame-retardant F polymer to a high degree, so the laminate is also excellent in flame retardancy. The F powder in this method preferably contains F polymer. The content of the F polymer in the powder is preferably 80% by mass or more, more preferably 100% by mass. As other components that can be included in the F powder, polymers and inorganic substances different from the F polymer can be mentioned.

Examples of polymers different from the F polymer include aromatic polyester, polyamide imide, thermoplastic polyimide, polyphenylene ether, and polyoxyxylene. Examples of inorganic substances include: silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, alkali aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, magnesium metasilicate ( Talc). The F powder containing the above-mentioned components preferably has a core-shell structure with an F polymer as a core and the above-mentioned components as a shell; or a core-shell structure with an F polymer as a shell and the above-mentioned components as a core. This F powder is obtained, for example, by cohesive (collision, aggregation, etc.) between F polymer powder and the powder of the above-mentioned components.

The D50 of the F powder is preferably 40 μm or less, more preferably 25 μm or less, and still more preferably 8 μm or less. The D50 of the F powder is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more. In this case, the dispersibility and handleability of the liquid composition are improved, and it is easy to further promote the compatibility of the F polymer and the cured product of the maleimide compound when the polymer layer is formed. The D90 of the F powder is preferably 15 μm or less, more preferably 10 μm or less. In other words, the F powder preferably does not contain coarse particles (particles of F polymer with a particle size of 10 μm or more or 15 μm or more). In this case, it is easy to further promote the compatibility of the F polymer and the cured product of the maleimide compound when forming the polymer layer. The content of the F powder in the liquid composition in this method is preferably 5% by mass or more, more preferably 10% by mass or more. The content of the F powder is preferably 50% by mass or less, more preferably 30% by mass or less. In this case, the dispersibility and handleability of the liquid composition become excellent, and it is easy to further promote the compatibility of the F polymer and the cured product of the maleimide compound when the polymer layer is formed.

The F polymer in this method is a polymer having a melting temperature of 260°C or higher and containing units (TFE units) based on tetrafluoroethylene (TFE). Examples of F polymers include: polytetrafluoroethylene (PTFE), copolymer of TFE and ethylene (ETFE), copolymer of TFE and propylene, copolymer of TFE and perfluoro(alkyl vinyl ether) (PAVE) (PFA), TFE and hexafluoropropylene (HFP) copolymer (FEP). The above-mentioned copolymer may further include units based on other comonomers. Furthermore, in addition to homopolymers containing TFE, PTFE also contains a very small amount of copolymers of comonomers (PAVE, HFP, FAE, etc.) and TFE (so-called modified PTFE). The modified PTFE preferably contains 99.5 mol% or more of TFE units relative to the total unit, and more preferably contains 99.9 mol% or more of TFE units.

As the F polymer, a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit (PAVE unit) and a hexafluoropropylene-based unit (HFP unit) is preferred. The F polymer in this case may include both the PAVE unit and the HFP unit, or only any one of them. As PAVE, CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ and CF ₂ =CFOCF ₂ CF ₂ CF ₃ (PPVE) are preferred, and PPVE is more preferred. The F polymer may have a polar functional group (oxygen-containing polar group). The polar functional group may be contained in the unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. As the latter form, examples include: F polymer having a polar functional group as a terminal group derived from a polymerization initiator, chain transfer agent, etc.; Functional group F polymer.

Considering the compatibility between the F polymer and the cured product of the maleimide compound when forming the polymer layer, the polar functional group is preferably a hydroxyl group-containing group and a carbonyl group-containing group, and is dispersed from a liquid composition In terms of sex, a carbonyl group-containing group is more preferable. The hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, more preferably -CF ₂ CH ₂ OH and -C(CF ₃ ) ₂ OH. The group containing a carbonyl group is a group containing a carbonyl group (>C(O)), preferably: a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a urethane group (-OC(O)NH ₂ ), acid anhydride residues (-C(O)OC(O)-), imine residues (-C(O)NHC(O)- etc.) and carbonate groups (-OC(O)O-). The number of carbonyl-containing groups in the F polymer is preferably ^{10 to 5000 per 1×10 6} carbons in the main chain, more preferably 100 to 3000, and still more preferably 800 to 1500. Furthermore, the number of carbonyl-containing groups in the F polymer can be quantified according to the composition of the polymer or the method described in International Publication No. 2020/145133.

The F polymer is preferably a polymer that contains TFE units and PAVE units, contains 1.5-5.0 mol% of PAVE units relative to the total units, and has a melting temperature of 280-320°C. As the F polymer, the polymer (1) and the polymer (2) are preferred, and the polymer (1) is more preferred. The polymer (1) includes a TFE unit and a PAVE unit, and has a polar functional group; The substance (2) contains TFE units and PAVE units, contains 2.0-5.0 mol% of PAVE units relative to the total units, and does not have a polar functional group. In this case, it is easy to form crystallites when the polymer is formed, and it is easy to further promote the compatibility of the F polymer and the cured product of the maleimide-based compound when the polymer layer is formed.

As the polymer (1), a polymer containing a TFE unit, a PAVE unit, and a unit based on a monomer having a polar functional group is preferred. The polymer preferably contains 90-99 mol% of TFE units, 0.5-9.97 mol% of PAVE units, and 0.01-3 mol% of units based on monomers with polar functional groups, relative to the total units. . In addition, as the monomer having a polar functional group, preferably: itaconic acid anhydride, citraconic acid anhydride, and 5-norene-2,3-dicarboxylic acid anhydride (another name: bicycloheptene dicarboxylic acid anhydride; hereinafter also referred to as "NAH"). As a specific example of the polymer (1), the polymer described in International Publication No. 2018/16644 can be cited.

The polymer (2) is preferably composed only of TFE units and PAVE units, and contains 95.0-98.0 mol% of TFE units and 2.0-5.0 mol% of PAVE units relative to the total units. The content of the PAVE unit in the polymer (2) is preferably 2.1 mol% or more with respect to the total units, more preferably 2.2 mol% or more. Furthermore, the so-called polymer (2) without polar functional groups means that the number of polar functional groups contained in the polymer is less than 500 ^{per 1×10 6 carbon atoms constituting the main chain of the polymer.} The number of the aforementioned polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of the aforementioned polar functional groups is usually zero. Polymer (2) can be produced by using polymerization initiators or chain transfer agents that do not generate polar functional groups as the end groups of the polymer chain, and can also be used for F polymers with polar functional groups (in the main chain The terminal group has a polar functional group derived from the polymerization initiator, etc.) by fluorination treatment. As a method of fluorination treatment, a method using fluorine gas can be exemplified (refer to Japanese Patent Laid-Open No. 2019-194314, etc.).

The melting temperature of the F polymer is 260°C or higher, preferably 275 to 325°C, more preferably 280 to 320°C. In this case, the F polymer and the maleimide-based compound are uniformly distributed in the polymer layer, and the electrical properties, peel strength, and low linear expansion of the laminate become excellent. The glass transition temperature of the F polymer is preferably 75 to 125°C, more preferably 80 to 100°C.

The maleimine compound in this method is a compound having a maleimine group (a monovalent group represented by the following formula (1)) and an aryl group. [化1]

The maleimide compound preferably contains 2 or more maleimine groups, more preferably 2-10 maleimine groups, and still more preferably 2 to 4 maleimine groups. base. The maleimide-based compound may be in the form of an oligomer or in the form of a polymer. In this case, the maleimide group may exist only in the terminal group, may exist only in the side chain, or may exist in both the terminal group and the side chain.

As the arylene group of the maleimide compound, phenylene and naphthylene are preferred, and phenylene is more preferred. The hydrogen atom of the aryl group of the maleimide compound can be replaced by other atoms or groups of atoms. In addition, the hydrogen atom of the aryl group may be substituted by a maleimino group. The maleimide-based compound preferably contains two or more phenylene groups. In this case, it is easy to further reduce the polarity of the maleimide-based compound and its cured product by the initial heating, and the compatibility with the F polymer in the later heating is improved, thereby easily improving the physical properties of the laminate. In addition, the UV (Ultraviolet) absorption of the laminate is improved, and the UV laser processability is improved, making it easy to process the laminate into a printed wiring board.

[式(2)中，Q為具有伸芳基之n價有機基，n為2～4之整數]The maleimide compound may be one type or a mixture of two or more types. The maleimide-based compound is preferably a compound represented by the following formula (2). [化2]

[In formula (2), Q is an n-valent organic group having an aryl extension, and n is an integer of 2 to 4]

The content of the maleimide compound in the liquid composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. The content of the maleimide-based compound is preferably 10% by mass or less, and more preferably 5% by mass or less. The ratio (mass ratio) of the content of the maleimine compound in the liquid composition to the content of the F polymer is preferably 0.001 or more, more preferably 0.01 or more. The above-mentioned comparison is preferably 0.2 or less, and more preferably 0.15 or less. In this case, when the polymer layer is formed, it is easy to form a polymer layer in which the hardened product of the maleimide compound is surrounded by the molten F polymer, so that the F polymer is used as the sea to harden The thing is the dense island structure of the island. As a result, in the laminate, the physical properties of the F polymer and the thermosetting product of the maleimide compound are more balanced, and the electrical properties, peel strength, warpage resistance, flame retardancy and other physical properties of the laminate are more balanced. Easy to improve.

It is preferable that the maleimide-based compound has a glass transition temperature of the cured product below the melting temperature of the F polymer. Specifically, the glass transition temperature of the cured product of the maleimide compound is preferably 100 to 250°C. In this case, the F polymer and the maleimide-based compound are uniformly distributed in the polymer layer, and the electrical properties, peel strength, and low linear expansion of the laminate become excellent. The molecular weight of the maleimide compound is preferably 300-2000, more preferably 500-1500. In this case, the cured product of the F polymer and the maleimide compound is uniformly distributed in the polymer layer, and the electrical properties, peel strength, and low linear expansion of the laminate become excellent.

The liquid composition in this method preferably contains a liquid dispersion medium. The liquid dispersion medium is a liquid compound that functions as a dispersion medium of the F powder and the maleimide compound and is inert at 25°C. The liquid dispersion medium may be one type or a mixture of two or more types. In the case of a mixture, it is preferable that different types of liquid compounds are compatible. The boiling point of the liquid dispersion medium is preferably 125 to 250°C. In this case, when the liquid dispersion medium is removed from the liquid composition during the initial heating, the F powder flows and is easily densely filled. As a liquid dispersion medium, considering the adjustment of the liquid properties (viscosity, thixotropy ratio, etc.) of the liquid composition and the solubility of the maleimide-based compound, an organic solvent (organic compound) is preferred. In consideration of the dispersion stability of the composition, it is preferably one or more liquid compounds selected from the group consisting of amides, ketones and esters, more preferably N-methyl-2-pyrrolidone and γ-butanone. Lactone, cyclohexanone and cyclopentanone. The content of the liquid dispersion medium in the liquid composition is preferably 30% by mass or more, more preferably 50% by mass or more. The content of the liquid dispersion medium is preferably 90% by mass or less.

In order to further improve the low linear expansion of the laminate, the liquid composition in this method preferably further contains an inorganic filler. As inorganic fillers, nitride fillers and inorganic oxide fillers are preferred, and boron nitride fillers, beryllium oxide fillers (beryllium oxide fillers), silicate fillers (silica fillers, wollastonite fillers, and talc) are more preferred. Filler), and metal oxide (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) fillers, and more preferably silica fillers. The content of silica in the inorganic filler is preferably 50% by mass or more, more preferably 75% by mass. The content of silicon oxide is preferably 100% by mass or less.

The inorganic filler is preferably surface-treated at least a part of its surface. The surface treatment agent used for the surface treatment may, for example, be polyols (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters, alkanolamines, Amine (trimethylamine, triethylamine, etc.), paraffin, silane coupling agent, silicone, polysiloxane. As the silane coupling agent, preferred are: 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Oxysilane, 3-methacryloxypropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane.

The average particle size of the inorganic filler is preferably 20 μm or less, more preferably 10 μm or less. The average particle size is preferably 0.1 μm or more, more preferably 1 μm or more. The shape of the inorganic filler may be any of granular, needle-shaped (fibrous), and plate-shaped. The specific shape of the inorganic filler can be exemplified: spherical, scaly, layered, leaf-shaped, almond-shaped, columnar, chicken crown, equiaxed, leaf-shaped, mica-shaped, massive, flat, wedge-shaped Shaped, rosette-shaped, net-shaped, angular columnar. Specific examples of inorganic fillers include: silica fillers ("ADMAFINE" series manufactured by ADMATECHS, etc.), zinc oxide surface-treated with esters such as propylene glycol dicaprate (manufactured by Sakai Chemical Industry Co., Ltd.) FINEX” series, etc.), spherical fused silica (“SFP” series manufactured by DENKA, etc.), coated with polyols and inorganic substances (“TIPAQUE” series manufactured by Ishihara Sangyo Co., Ltd.), and treated with alkyl silane Surface treatment of rutile titanium dioxide ("JMT" series manufactured by Teikoku Chemical Co., Ltd.), hollow silica filler ("E-SPHERES" series manufactured by Pacific Cement Co., Ltd., "SILINAX" series manufactured by Nippon Steel Mining Co., Ltd., "ECCO SPHERE" series manufactured by EMERSON & CUMING), talc fillers ("SG" series manufactured by Japanese Talc Company, etc.), lump talc fillers ("BST" series manufactured by Japanese Talc Company, etc.), boron nitride fillers ( "UHP" series manufactured by Showa Denko Corporation, "DENKA BORON NITRIDE" series manufactured by Denka Corporation ("GP", "HGP" grades, etc.).

The content of the inorganic filler in the liquid composition is preferably 1% by mass or more, more preferably 3% by mass or more. The content of the inorganic filler is preferably 30% by mass or less, more preferably 20% by mass or less. The ratio (mass ratio) of the content of the inorganic filler to the content of the F polymer in the liquid composition is preferably 0.01 or more, more preferably 0.1 or more. The above-mentioned comparison is preferably 1 or less, and more preferably 0.8 or less.

In order to further improve the bendability of the laminate, the liquid composition in this method preferably further contains an elastomer. The elastomer is preferably a thermoplastic elastomer, more preferably: butene-based elastomer, diene-based elastomer (isoprene-based elastomer, butadiene-based elastomer, etc.), styrene-based elastomer, Acrylic elastomer, silicone elastomer and fluorine elastomer.

The styrene-based elastomer may, for example, be styrene-butadiene copolymer, hydrogenated-styrene-butadiene copolymer, hydrogenated-styrene-isoprene copolymer, styrene-butadiene- Styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene Hydrogenated block copolymers, etc. In order to improve the adhesion with the F polymer, the elastomer is preferably modified to have a functional group. The functional group may, for example, be an epoxy group, a carbonyl group-containing group, a hydroxyl group, an isocyanate group, or an amino group. The glass transition temperature of the elastomer is preferably 10°C or less, more preferably 5°C or less. In this case, it is easy to further improve the bendability of the laminate. In addition, the elastomer may be soluble in the liquid dispersion medium or may be insoluble, but preferably has solvent solubility.

Specific examples of elastomers include liquid rubbers such as polybutadiene, polystyrene, butadiene-acrylonitrile copolymer (NBR); two-terminal carboxyl butadiene-acrylonitrile copolymer (CTBN), Reactive liquid rubber such as aminobutadiene-acrylonitrile copolymer (ATBN) at both ends; silicone rubber such as polydimethylsiloxane with amine groups or epoxy groups on both ends or side chains; cross-linked NBR particles , Cross-linked silicone particles, acrylic core-shell particles and other particulate rubbers. The content of the elastomer in the liquid composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. The content of the elastomer is preferably 10% by mass or less, more preferably 5% by mass or less. The ratio (mass ratio) of the content of the elastomer to the content of the F polymer in the liquid composition is preferably 0.001 or more, more preferably 0.01 or more. The above-mentioned comparison is preferably 0.2 or less, and more preferably 0.15 or less.

The liquid composition in this method may further include components that promote the hardening of the maleimide compound (radical polymerization initiator, imidazole hardener, cationic hardener, or copolymerizable other crosslinking monomer Wait). In this case, it is easy to control the partial hardening (reaction) of the maleimide-based compound during the initial heating, and the formation of the F polymer and the cured product of the maleimine-based compound are mutually dissolved during the later heating. Polymer layer.

Examples of the component include imidazole (2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyano Ethyl-2-ethyl-4-methylimidazole, etc.), secondary or tertiary amines (triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, tris(dimethylamine) Methyl)phenol, dimethylbenzylamine, etc.), amidines (1,8-diaza-heterobicyclo(5,4,0)-7-undecene, etc.), phosphines (triphenylphosphine, tributylphosphine, etc.) , Trioctyl phosphine, etc.), organic metal salts (stannous octoate, zinc octoate, dibutyl tin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, etc.), metal chlorides (lithium chloride, Zinc chloride, aluminum chloride, tin chloride, etc.), organic peroxides (tertiary butyl peroxide, dicumyl peroxide, etc.), azo compounds (azobisisobutyronitrile, azo Nitrogen bisdimethylvaleronitrile, etc.), mineral acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), alkali metal carbonates (sodium carbonate, etc.).

To improve dispersibility and handling properties, the liquid composition in this method may further include a surfactant. The surfactant is preferably nonionic. The hydrophilic part of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group. The oxyalkylene group may contain one kind or two or more kinds. In the latter case, the oxyalkylene groups of different types can be arranged randomly or in block. The oxyethylene group is preferably oxyethylene group.

The hydrophobic part of the surfactant preferably has an ethynyl group, a polysiloxyalkyl group, a perfluoroalkyl group or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant. Among them, the surfactant is more preferably a fluorine-based surfactant, and still more preferably a fluorine-based surfactant having a hydroxyl group (especially an alcoholic hydroxyl group) or an oxyalkylene group, and a perfluoroalkyl group or a perfluoroalkenyl group. Specific examples of the surfactant include: "FTERGENT" series (manufactured by NEOS), "SURFLON" series (manufactured by AGC Seimi Chemical Co., Ltd.), "MEGAFAC" series (manufactured by DIC Corporation), "UNIDYNE" series ( Daikin Industry Co., Ltd.). The content of the surfactant in the liquid composition is preferably 1 to 15% by mass. In this case, the affinity between the components is likely to increase sharply.

The viscosity of the liquid composition in this method at 25°C is preferably 50 mPa·s or more, more preferably 100 mPa·s or more. The viscosity of the liquid composition is preferably 5000 mPa·s or less, more preferably 1000 mPa·s or less. The thixotropic ratio of the liquid composition in this method is preferably 1.0 to 2.0. In order to control the hardening (reaction) of the maleimide compound, the pH of the liquid composition in this method is preferably 7 or less.

The liquid composition in this method may further contain other resins. Other resins can be thermosetting resins or thermoplastic resins. Examples of other resins include epoxy resin, maleimide resin, polyurethane resin, polyimide, polyamide acid, polyamide imide, polyphenylene ether, polyoxyxylene, liquid crystal poly Ester, fluorine-containing polymer other than F polymer. The liquid composition may also contain in addition to the above-mentioned components: a thixotropy imparting agent, a defoamer, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, Additives such as brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity regulators, flame retardants, etc.

As the substrate layer in this method, a metal substrate (metal foil such as copper, nickel, aluminum, titanium, alloys thereof, etc., etc.), a polymer film (polyimide, polyarylate, polyether, poly Arylene, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystal polyester, liquid crystal polyesteramide, etc. film), prepreg (fiber reinforced The resin substrate precursor), more preferably metal foil and polymer film. The application of the liquid composition to the surface of the substrate layer is preferably performed by coating. The coating method may, for example, be spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, contact coating method, bar coating method , Die nozzle coating method, injection-Meller bar method, slit die nozzle coating method.

The initial heating temperature in this method is a temperature above 100°C and below the melting temperature of the F polymer. The initial heating temperature is preferably 150 to 250°C, more preferably 180 to 220°C. In this case, it is easier to control the partial hardening (reaction) of the maleimide compound in the initial heating. Furthermore, as the partial hardening (reaction) of the maleimide-based compound, a reaction (condensation reaction, addition reaction, etc.) accompanied by a ring-opening reaction of the maleimine group can be exemplified. The heating time for the initial heating is preferably 1 to 10 minutes. In this method, the subsequent heating temperature is a temperature above the melting temperature of the F polymer. The later heating temperature is preferably 300-400°C, more preferably 320-380°C. In this case, it is easy to melt the F polymer powder to a higher degree, and it is easy to further dissolve it with the cured product of the maleimide compound to form a polymer layer. The heating time of the post-heating is preferably 1-10 minutes.

As the heating method in the initial heating and the post heating, there can be mentioned: the method of using an oven, the method of using a ventilated drying furnace, the method of irradiating hot rays such as infrared rays. The thickness of the polymer layer in this method is preferably 0.1-150 μm. Specifically, if the substrate layer is a metal foil, the thickness of the polymer layer is preferably 1-30 μm. If the substrate layer is a polymer film, the thickness of the polymer layer is preferably 5-50 μm.

The liquid composition in this method may be applied to only one surface of the substrate layer, or the liquid composition in this method may be applied to both surfaces of the substrate layer. In the former case, a laminate having a substrate layer and a polymer layer formed on one surface of the substrate layer can be obtained. In the latter case, a laminate having a substrate layer and a polymer layer formed on the substrate layer can be obtained. A laminate of polymer layers on both surfaces. The latter laminate is less likely to warp, so it has excellent workability. As a specific example of the laminate, a metal-clad laminate having a metal foil and a polymer layer formed on at least one surface of the metal foil; a multilayer film having a polyimide film and forming Polymer layers on both surfaces of the polyimide film. These laminates are excellent in various physical properties such as electrical characteristics, and are therefore suitable as printed circuit board materials and the like. Specifically, the laminate can be used to manufacture a flexible printed circuit board or a rigid printed circuit board.

The liquid composition of the present invention (hereinafter, also referred to as "this composition") is a liquid composition containing a tetrafluoroethylene-based polymer powder containing a TFE unit and a PAVE unit, and a maleimide-based compound. The tetrafluoroethylene-based polymer in this composition contains TFE units and PAVE units, and has a polar functional group; or, the tetrafluoroethylene-based polymer in this composition contains TFE units and PAVE units. A polymer containing 2.0-5.0 mol% of the above-mentioned PAVE-based unit in the total unit and having no polar functional group (hereinafter, also collectively referred to as "PFA-based polymer"). This composition is a dispersion liquid obtained by dispersing the powder of the PFA-based polymer and dispersing or dissolving the maleimide-based compound to a high degree. The composition has excellent dispersibility and handling properties. Although the reason is not necessarily clear, the inventors of the present invention consider it as follows.

Maleimine compounds can be described as not only polar compounds, but also compounds with hydrophilic sites (maleimine groups) and hydrophobic sites (aryl groups), so they are considered to have the viscosity of a liquid composition The effect and the effect of reducing the surface tension of the liquid composition (interface activity effect). If the liquid composition in a state containing the compound contains a PFA-based polymer with a specific structure among a tetrafluoroethylene-based polymer with a substantially lower polarity and surface tension (PFA-based polymer with a polar functional group; or PAVE unit content is higher, does not have polar functional group, and the degree of freedom of the polymer chain is higher (PFA polymer) powder, it is considered that it is easy to synergistically and balancely show the obtained by maleimide compound The above-mentioned effects (tackification and interfacial activity). As a result, the precipitation and foaming of the powder are suppressed, and the thickening of the composition is completed. Therefore, it is considered that a liquid composition (this composition) excellent in dispersibility and handling properties can be obtained. In addition, when PFA-based polymers are formed into molded products (polymer layers in this method, etc.), they are easy to form tiny spherulites and are highly compatible with the cured products of maleimide-based compounds. Therefore, if you use this combination It is easy to obtain a molded product having the physical properties of a PFA-based polymer and a maleimide-based compound to a high degree.

The form of the PFA-based polymer powder in the composition is the same as the form of the powder in the above-mentioned method, and its preferred form is also the same. The PFA-based polymer in the composition is the polymer (1) or the polymer (2) in the above-mentioned method, and the preferred range is also the same as its equivalent range. In order to more easily exhibit the above-mentioned effects, the polar functional group in the polymer (1) is preferably a hydroxyl group-containing group and a carbonyl group-containing group, and more preferably a carbonyl group-containing group. The form of the maleimine compound in this composition is the same as the form of the maleimine compound in the above-mentioned method, and its preferred form is also the same.

If the maleimine-based compound has two or more maleimine groups and two or more arylene groups, it is easier to exhibit the above-mentioned effects. The ratio (mass ratio) of the content of the maleimide-based compound in the composition to the content of the PFA-based polymer is preferably 0.001 or more, more preferably 0.01 or more. The above-mentioned comparison is preferably 0.2 or less, and more preferably 0.15 or less. If a maleimide-based compound is contained in this ratio, it is not only easier to exhibit the above-mentioned effects, but also it is easy to form a PFA-based polymer as a sea in the formed molded product, and a maleimine-based compound The hardened product is the dense sea-island structure of the island, so it is easy to obtain a molded product with a high degree of physical properties of both.

The present composition preferably contains a liquid dispersion medium. The form of the liquid dispersion medium, including preferred forms, is the same as the liquid dispersion medium in this method. The present composition preferably further contains an inorganic filler. The form of the inorganic filler, including the preferred form, is the same as that of the inorganic filler in this method. The present composition preferably further contains an elastomer. The shape of the elastomer, including the preferred shape, is the same as that of the elastomer in this method.

The composition may further include: components to further promote the curing reaction of the maleimide compound, surfactants, other resins, and other additives (thixotropy imparting agent, defoaming agent, silane coupling agent, dehydrating agent, plasticizing agent, etc.) Agents, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity regulators, flame retardants, etc.). The forms of these components, including preferred forms, are the same as those in this law. The forming components of the molded article in this composition (when it contains inorganic fillers, elastomers, other resins (polymers) or other additives in addition to PFA-based polymers and maleimide-based compounds, it includes The total content of them) is preferably 30% by mass or more, more preferably 50% by mass or more. The above-mentioned total content is preferably 80% by mass or less. Even if the content of the forming components of the molded article is large, the dispersibility and handling properties of the composition are excellent due to the above-mentioned effects.

The viscosity of the composition at 25°C is preferably 50 mPa·s or more, more preferably 100 mPa·s or more. The viscosity of the composition at 25°C is preferably 5000 mPa·s or less, more preferably 1000 mPa·s or less. The thixotropy ratio of the composition at 25°C is preferably 1.0 to 2.0. In view of the curability (reactivity) of the maleimide-based compound, the present composition is preferably acidic.

The composition can be used to form a layer with the adhesiveness of the cured product derived from the maleimide compound and the higher gas barrier properties derived from the F polymer. Therefore, the present composition can also be used as a heat sealant for packaging films (pillow packaging films, etc.) and the like. The composition is particularly useful as a heat sealant for packaging materials for products (food, chemicals, etc.) that are prone to quality deterioration due to water vapor or oxygen. Specifically, the composition can be used as packaging materials for snacks and other foods, or packaging materials for food cups and food trays, or packaging materials for pharmaceutical and agricultural products, or packaging materials for chemical products, or packaging for precision electronic parts such as semiconductors. Heat sealant for materials. At this time, the composition may contain an adhesive and an antistatic agent.

When using this composition as a heat sealant, it is only necessary to apply the composition to the base material of the packaging material and use it. For example, as long as two pieces of packaging materials are prepared, the present composition is applied to at least one sealing part, and the two pieces are overlapped and heated with a heat sealer, the two pieces of packaging materials can be heat-sealed. As the material of the substrate, paper pulp, metal, plastic, and glass can be cited. The structure of the substrate is preferably a structure having a substrate layer and a gas barrier layer. The barrier layer may include a water-soluble polymer (polyvinyl alcohol, etc.) and a crosslinking agent. The substrate layer may be formed of only the material of the above-mentioned substrate, or may include a plurality of materials of the above-mentioned substrate. Specific examples of the former include paper, metal foil, and plastic film. As the latter form, a laminate of paper and plastic, a laminate of plastic film and aluminum foil, and a laminate of different types of plastic films can be mentioned. The base material layer may further have a vapor-deposited layer of inorganic oxides such as aluminum, silicon oxide, and aluminum oxide. Example

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited by them. The following materials are used in the examples. [Powder] Powder 1: Containing 97.9 mol% of TFE units, 0.1 mol% of NAH units, and 2.0 mol% of PPVE units, and having a polar functional group polymer 1 (melting temperature: 300 ℃) Composition powder (D50: 2.1 μm) Powder 2: A powder composed of polymer 2 (melting temperature 305°C) that contains 98.7 mol% of TFE units and 1.3 mol% of PPVE units and does not have polar functional groups (D50: 1.8 μm) In addition, the polymer 1 system has 1000 carbonyl-containing groups ^{per 1×10 6 carbon atoms in the main chain.}

[Maleimide compounds] Maleimide 1: Compound with maleimide group and phenylene Furthermore, maleimide 1 is a mixture of compounds having 2 to 4 maleimide groups and a plurality of phenylene groups, and its number average molecular weight is 800, and the glass transition temperature of its cured product is 280°C. [Liquid dispersion medium] NMP: N-methyl-2-pyrrolidone

[Surfactant] Surfactant 1: CH ₂ =C(CH ₃ )C(O)OCH ₂ CH ₂ (CF ₂ ) ₆ F and CH ₂ =C(CH ₃ )C(O)(OCH ₂ CH ₂ ) ₂₃ OH copolymer [inorganic filler] Filler 1: Silica filler (D50: 5.2 μm) [Elastomer] Elastomer 1: Amine modified styrene elastomer (SEBS, manufactured by Asahi Kasei Corporation, "TUFTEC MP10")

(Example 1) Manufacturing example of liquid composition (Example 1-1) Surfactant 1 is put into a solution containing maleimine 1 and NMP, and elastomer 1 and filler 1 are put in order, and stirred to prepare a mixed solution. In addition, surfactant 1 and powder 1 were put into NMP and stirred to prepare a dispersion. These mixed liquids and dispersion liquids are mixed and stirred to obtain a liquid composition 1 (viscosity: 500 mPa·s), which contains: powder 1 (30 parts by mass) and maleimide 1 (3 parts by mass) , Elastomer 1 (3 parts by mass), Filler 1 (15 parts by mass), Surfactant 1 (4 parts by mass), and NMP (45 parts by mass). The liquid composition 1 is a dispersion in which the powder 1 is dispersed. (Example 1-2~Example 1-5) Except for changing the type and amount of each component as shown in Table 1 below, the liquid compositions 2 to 5 were obtained in the same manner as in Example 1-1.

[Table 1] Liquid composition number powder Maleimide compounds Inorganic filler Elastomer Surfactant NMP 1 1(30) 1(3) 1(15) 1(3) 1(4) 45 2 1(30) 1(3) -(0) -(0) 1(4) 63 3 1(30) 1(3) -(0) -(0) -(0) 67 4 2(30) 1(3) -(0) -(0) 1(4) 63 5 2(30) 1(3) 1(15) 1(3) 1(4) 45 ※The value in the brackets in each column refers to the content in the liquid composition (unit: mass%).

The relevant evaluation results of the dispersion stability, handling properties, viscosity, and thixotropy ratio of the obtained liquid composition are summarized and shown in Table 2 below. Furthermore, the dispersion stability and handling properties were evaluated according to the following methods.

[Dispersion stability] After storing the storage liquid composition at 25°C, the dispersibility was confirmed visually, and the dispersion stability was evaluated based on the following criteria. [Assessment criteria] ○: No deposit is recognized. △: Although the precipitate is visually recognized, it can be easily dispersed again. ×: A precipitate is visually recognized, and it is difficult to disperse again.

[Handling] When preparing the liquid composition, visually confirm the foaming state when the mixed liquid and the dispersion liquid are mixed, and evaluate it based on the following criteria. [Assessment criteria] ○: Foaming disappeared within 3 hours after preparation. ×: After preparation, foaming did not disappear even after 3 hours.

[Table 2] Liquid composition number Dispersion stability Handleability Viscosity (mPa.s) Thixotropy ratio 1 ○ ○ 500 1.2 2 ○ ○ 400 1.1 3 ○ ○ 800 1.1 4 △ X 600 1.1 5 X X ＞5000 -

(Example 2) Manufacturing example of laminated body (Example 2-1) Manufacturing example of laminated body 1 The liquid composition 1 was applied to the surface of a long copper foil (thickness: 18 μm) using a bar coater to form a wet film. Then, the initial heating temperature was set to 200° C., and the metal foil formed with the wet film was heated in a nitrogen oven for 5 minutes. Then, set the post-heating temperature to 380°C and heat it in a nitrogen oven for 3 minutes. Thereby, a laminate 1 having a metal foil and a polymer layer 1 (thickness: 5 μm), which is a cured product of the F polymer 1, maleimide 1, and the surface of the metal foil, was obtained. Filler 1 and elastomer 1.

(Example 2-2) Manufacturing example of laminate 2 Except that the type of the liquid composition used was changed to the liquid composition 2, the layered product 2 was obtained from the liquid composition 2 in the same manner as in Example 2-1. (Example 2-3) Manufacturing example of laminate 5 Except that the temperature of the initial heating was set to 100°C, a laminate 5 was obtained in the same manner as in Example 2-1. (Example 2-4) Manufacturing example of laminated body 6 Except for omitting the initial heating, a laminate 6 was obtained in the same manner as in Example 2-1.

Table 3 summarizes the evaluation results of the dielectric loss factor, peel strength, linear expansion coefficient, and bendability of each laminate, and the evaluation results of the transmission characteristics of the printed wiring board obtained by processing each laminate. Furthermore, the evaluation of each is carried out according to the following methods.

[Dielectric loss factor] The copper foil of the laminate was removed by etching with a ferric chloride aqueous solution to produce a single polymer layer, and the measurement was performed by SPDR (Separation Column Dielectric Resonance) method at a measurement frequency of 10 GHz. [Assessment criteria] ○: The dielectric loss factor is less than 0.0012. △: The dielectric loss factor is 0.0012 or more and 0.0024 or less. ×: The dielectric loss factor exceeds 0.0024.

[Peel strength] Cut out a rectangular test piece (length 100 mm, width 10 mm) from the laminate. Then, fix the position 50 mm away from one end of the long side direction of the test piece, and at a stretching speed of 50 mm/min, peel off the copper foil and polymer at an angle of 90° with respect to the test piece from one end of the long side direction.物层。 The material layer. The maximum load at this time was measured as the peel strength (N/cm). [Assessment criteria] ○: The peel strength is 8 N/cm or more. △: The peel strength is 4 N/cm or more and less than 8 N/cm. ×: The peel strength is less than 4 N/cm.

[Linear expansion coefficient] The copper foil of the laminate was removed by etching with ferric chloride aqueous solution to produce a single polymer layer, and a 180 mm square test piece was cut out. Then, the coefficient of linear expansion of the test piece within the range of 25°C to 260°C is measured according to the measurement method specified in JIS C 6471:1995. [Assessment criteria] ○: 30 ppm/℃ or less. △: More than 30 ppm/°C and 50 ppm/°C or less. ×: More than 50 ppm/°C.

[Bendability] The copper foil of the laminate was removed by etching with ferric chloride aqueous solution to produce a single polymer layer, and a square test piece of 5 mm square test piece was cut out. Then, bend 180° under the condition of the radius of curvature (300 μm), apply a load (50 mN, 1 minute) from above to restore the bending, and evaluate the appearance of the test piece according to the following criteria. [Assessment criteria] ○: No abnormal appearance is seen in the crease. △: Whitening is found in the crease part. ×: Breakage occurred at the crease.

The transmission characteristics of the printed circuit board obtained by processing the laminated body obtained are measured and evaluated according to the following methods. [Transmission characteristics] A transmission line is formed on the copper foil of the laminate to make a printed wiring board. The formation of the transmission line uses a microstrip line. A vector network analyzer (manufactured by KEYSIGHT TECHNOLOGIE, "E8361A") was used to process the 28 GHz signal in the printed wiring board, and the Universal Test Fixture was used as a probe to measure the S21 parameter representing the transmission loss. At this time, the characteristic impedance of the line is set to 50 Ω, and the length of the transmission line of the printed wiring board is set to 50 mm to measure the transmission loss. Set the transmission loss scale to one of the network parameters used to express the characteristics of high-frequency electronic circuits or high-frequency electronic parts, namely "S21-parameter", and use it as the transmission loss value. Furthermore, the closer the value is to 0, the smaller the transmission loss. [Assessment criteria] ○: -0.7 or more and 0 or less. △: Less than -0.7 and greater than -1.0. ×: It did not reach -1.0.

[table 3] Layered body number Dielectric loss factor Peel strength Coefficient of linear expansion (ppm/℃) Flexibility Transmission characteristics 1 ○ ○ ○ ○ ○ 2 ○ ○ △ △ ○ 5 △ △ ○ ○ △ 6 X X X - -

The copper foil of the laminate was removed by etching with ferric chloride aqueous solution to produce a single polymer layer, and it was evaluated whether the polymer layer meets the UL94-V0 standard for flame retardancy. As a result, the polymer layers of laminates 1 and 2 met the standards, and the polymer layers of laminates 5 and 6 did not meet the standards. [Industrial availability]

According to the present invention, a molded product having physical properties based on a tetrafluoroethylene-based polymer and physical properties based on a maleimide-based compound can be obtained. The molded product obtained by the present invention can be used as antenna parts, printed circuit boards, aircraft parts, automotive parts, sports goods, food industry products, paints, cosmetics, etc., specifically, can be used as: wire coating materials (aircraft Electrically insulating tapes, insulating tapes for petroleum mining, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrodes Adhesives (for lithium secondary batteries, fuel cells, etc.), replica rollers, furniture, automobile dashboards, home appliances, etc., housings, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, etc.) Machines, conveyor belts for food conveying, etc.), tools (shovels, files, awls, saws, etc.), boilers, funnels, pipes, ovens, baking molds, chutes, mold nozzles, toilets, container covering materials.

Claims (15)

A method for manufacturing a laminate, which provides a liquid combination of a tetrafluoroethylene polymer powder with a melting temperature of 260°C or higher and a thermosetting compound having a maleimide group and an arylene group to the surface of a substrate layer The material is heated at a temperature above 100°C and below the melting temperature of the above-mentioned tetrafluoroethylene-based polymer, and further heated at a temperature above the melting temperature of the above-mentioned tetrafluoroethylene-based polymer to form a polymer layer, Thus, a laminate having the above-mentioned base material layer and the above-mentioned polymer layer is obtained. The manufacturing method of claim 1, wherein the above-mentioned tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing perfluoro(alkyl vinyl ether)-based units or hexafluoropropylene-based units. The manufacturing method of claim 1 or 2, wherein the above-mentioned tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a unit based on perfluoro(alkyl vinyl ether) and having a polar functional group; or, the above-mentioned tetrafluoroethylene-based polymer The vinyl fluoride polymer is a tetrafluoroethylene polymer that contains 2.0-5.0 mol% of perfluoro(alkyl vinyl ether)-based units with respect to the total unit and does not have a polar functional group. The production method according to any one of claims 1 to 3, wherein the liquid composition further includes an inorganic filler. The manufacturing method according to any one of claims 1 to 4, wherein the liquid composition further comprises an elastomer. The production method according to any one of claims 1 to 5, wherein the ratio of the content of the thermosetting compound in the liquid composition to the content of the tetrafluoroethylene-based polymer is 0.2 or less. The manufacturing method according to any one of claims 1 to 6, wherein the glass transition temperature of the cured product of the thermosetting compound is lower than the melting temperature of the tetrafluoroethylene-based polymer. The manufacturing method according to any one of claims 1 to 7, wherein the substrate layer is a metal foil or a polymer film. A liquid composition containing a tetrafluoroethylene polymer powder containing a unit based on perfluoro(alkyl vinyl ether), and a thermosetting compound having a maleimide group and an aryl group, and the above-mentioned tetrafluoroethylene The ethylene-based polymer has a polar functional group, or contains 2.0 to 5.0 mol% of the unit based on the above-mentioned perfluoro(alkyl vinyl ether) with respect to the total unit and does not have a polar functional group. The liquid composition according to claim 9, wherein the molecular weight of the thermosetting compound is 300-2000. The liquid composition of claim 9 or 10, wherein the average particle size of the tetrafluoroethylene polymer powder is 40 μm or less. The liquid composition according to any one of claims 9 to 11, which further contains an inorganic filler. The liquid composition according to any one of claims 9 to 12, which further comprises an elastomer. The liquid composition according to any one of claims 9 to 13, wherein the ratio of the content of the thermosetting compound in the liquid composition to the content of the tetrafluoroethylene-based polymer is 0.2 or less. The liquid composition according to any one of claims 9 to 14, wherein the viscosity of the liquid composition at 25°C is 100 to 5000 mPa·s.