Composition, molded article, laminate, and method for manufacturing the composition

Abstract

To provide: a composition which can prevent the aggregation of a fluororesin that causes a defect in the appearance of a strand even when the content of the fluororesin is increased; a molded article; a laminated body; and a method for producing a composition.SOLUTION: The present disclosure provides a composition comprising a fluororesin A and a resin B having a melt flow rate of 30 g / 10 min or more at a temperature higher by 8°C than the melting point thereof (excluding the fluororesin A), where the fluororesin A is a resin satisfying the formula: (MFR of the fluororesin A) / (MFR of the resin B)=0.2 to 10.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to compositions, molded articles, laminates, and methods for manufacturing compositions. [Background technology]

[0002] Various studies are underway regarding compositions containing fluororesins and liquid crystal polymers (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-187833 [Patent Document 2] Japanese Patent Publication No. 2018-177931 [Patent Document 3] Japanese Patent Publication No. 2019-065061 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The inventors' investigations revealed that, as demonstrated in the examples of Patent Documents 2 and 3, increasing the proportion of fluororesin reduces the affinity between the liquid crystal polymer and the fluororesin, making aggregation (poor dispersion) of the fluororesin more likely to occur. Since aggregation of fluororesin causes defects in the appearance of the strand, it is preferable to minimize its occurrence.

[0005] The present disclosure aims to provide a composition, a molded article, a laminate, and a method for producing the composition that can suppress the aggregation of fluororesin, which causes defects in the appearance of strands, even when the proportion of fluororesin is increased. [Means for solving the problem]

[0006] The present disclosure (1) includes a fluororesin A and a resin B (excluding the fluororesin A) having a melt flow rate of 30 g / 10 min or more at a melting point +8°C. The fluororesin A is a composition (hereinafter, also referred to as "the composition of the present disclosure") which is a resin satisfying MFR of the fluororesin A / MFR of the resin B = 0.2 to 10.

[0007] The present disclosure (2) is the composition according to the present disclosure (1), wherein the MFR of the fluororesin A is 30 g / 10 min or more.

[0008] The present disclosure (3) is the composition according to the present disclosure (1) or (2), wherein the fluororesin A is at least one selected from the group consisting of a tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer.

[0009] The present disclosure (4) is the composition according to any one of the present disclosures (1) to (3), wherein the resin B is at least one selected from the group consisting of a liquid crystal polymer, a polyetherimide, a polyphenylene sulfide, a polyaryl ether ketone, a polysulfone, and a polyether sulfone.

[0010] The present disclosure (5) is the composition according to any one of the present disclosures (1) to (4), wherein the content of the fluororesin A is 10% by volume or more.

[0011] The present disclosure (6) is the composition according to any one of the present disclosures (1) to (5), wherein the dispersed particle diameter of the fluororesin A is 5.0 μm or less.

[0012] The present disclosure (7) is the composition according to any one of the present disclosures (1) to (6), which contains an additive.

[0013] The present disclosure (8) is a molded article (hereinafter, also referred to as "the molded article of the present disclosure") containing the composition according to any one of the present disclosures (1) to (7).

[0014] This disclosure (9) is a molded article according to this disclosure (8) used in a low dielectric substrate material.

[0015] Disclosure (10) is a laminate comprising a metal foil and a molded article as described in Disclosure (8) or (9) (hereinafter also referred to as the "Laminate of the Disclosure").

[0016] The present disclosure (11) is the laminate according to the present disclosure (10), wherein the metal foil is copper.

[0017] (12) This disclosure is a method for producing a composition (hereinafter also referred to as "the method for producing this disclosure") which involves adjusting the ratio of (MFR of fluororesin A) / (MFR of resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 min or more at a melting point of +8°C) to 0.2 to 10 through an MFR adjustment step.

[0018] This disclosure (13) is a method for producing the composition according to this disclosure (12), wherein in the MFR adjustment step, the fluororesin A is obtained by polymerization, kneading, or irradiation with ionizing radiation. [Effects of the Invention]

[0019] According to this disclosure, it is possible to provide a composition, a molded article, a laminate, and a method for producing the composition that can suppress the aggregation of fluororesin, which causes defects in the appearance of strands, even when the proportion of fluororesin is increased. [Modes for carrying out the invention]

[0020] In this specification, "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of such "organic groups" are: Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and RaNRbSO2- (In these formulas, Ra is independent of, Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Rb is independently H or an alkyl group which may have one or more substituents. It includes. The above organic group is preferably an alkyl group which may have one or more substituents.

[0021] The following provides a detailed explanation of this disclosure.

[0022] <Compositions of this Disclosure> The composition of the present disclosure comprises a fluororesin A and a resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 min or more at a melting point of +8°C, wherein fluororesin A is a resin that satisfies the ratio of MFR of fluororesin A to MFR of resin B of 0.2 to 10.

[0023] According to the composition of this disclosure, the affinity between fluororesin A and resin B can be improved by adjusting the MFR of fluororesin A / resin B within the above range. As a result, even when the proportion of fluororesin is increased, aggregation of fluororesin, which causes defects in the appearance of the strand, can be suppressed.

[0024] Examples of fluororesin A include tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymer, CTFE / TFE / PAVE copolymer, Et / CTFE copolymer, polyvinyl fluoride [PVF], polyvinylidene fluoride [PVdF], vinylidene fluoride [VdF] / TFE copolymer, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / HFP / (meth)acrylic acid copolymer, VdF / CTFE copolymer, VdF / pentafluoropropylene copolymer, VdF / PAVE / TFE copolymer, TFE / perfluoroalkyl allyl ether copolymer, and the like. Perfluoroalkyl allyl ethers are CF2=CFCF2-O-Rf 4 (Rf 4 It is a monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms.

[0025] As for fluororesin A, from the viewpoint of affinity with resin B, at least one selected from the group consisting of tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] and tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP] is preferred, with FEP being more preferred.

[0026] The perfluorovinyl ether is not particularly limited; for example, the following general formula (1) CF2 = CF - ORf (1) Examples include perfluorounsaturated compounds represented by the formula (wherein Rf represents a perfluoroorganic group). In this specification, the term "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to a carbon atom are replaced with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0027] Examples of perfluorovinyl ethers include perfluoro(alkyl vinyl ether) [PAVE], in which Rf in general formula (1) represents a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0028] Examples of perfluoroalkyl groups in PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl groups, but purple oro(propyl vinyl ether) [PPVE], in which the perfluoroalkyl group is a perfluoropropyl group, is preferred.

[0029] As perfluorovinyl ethers, in general formula (1), Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is given by the following formula:

[0030] [ka]

[0031] (where m represents an integer of 0 or 1 to 4) and those which are groups represented by Rf is the following formula:

[0032]

Chemical formula

[0033] (where n represents an integer of 1 to 4) and the like.

[0034] (Perfluoroalkyl)ethylene is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene [PFHE], (perfluorooctyl)ethylene and the like.

[0035] Although PFA is not particularly limited, a copolymer in which the molar ratio of TFE units to PAVE units (TFE units / PAVE units) is 70 / 30 or more and less than 99 / 1 is preferable. A more preferable molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferable molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above PFA preferably has monomer units derived from monomers copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol% (a copolymer in which the total of TFE units and PAVE units is 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0036] Monomers copolymerizable with TFE and PAVE include HFP, formula (I): CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (where Z 1 Z 2 and Z 3 are the same or different and each represents a hydrogen atom or a fluorine atom, and Z 4) represents a vinyl monomer represented by formula (II): CF2=CF-OCH2-Rf 1 (In the formula, Rf 1 CZ represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) Alkyl perfluorovinyl ether derivatives represented by formula (X):CZ 5 Z 6 =CZ 7 -CZ 8 Z 9 -O-Rf 4 (in the formula, in the formula, Z 5 , Z 6 and Z 7 Z represents a hydrogen atom, a chlorine atom, or a fluorine atom, either identical or different. 8 and Z 9 Rf represents a hydrogen atom or a fluorine atom. 4 CH2=CFCF2-O-Rf 4 CF2 = CFCF2 - O - Rf 4 (Perfluoroalkyl allyl ether), CF2=CFCH2-O-Rf 4 CH2=CHCF2-O-Rf 4 (In the formula, Rf 4 Examples of which are the same as in formula (X) above include: Furthermore, monomers copolymerizable with TFE and PAVE include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and acid anhydrides of unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.

[0037] PFA is preferably melted at 180 to less than 324°C, more preferably at 230 to 320°C, and even more preferably at 280 to 320°C.

[0038] While not particularly limited, copolymers with a molar ratio of TFE units to HFP units (TFE units / HFP units) of 70 / 30 or more and less than 99 / 1 are preferred. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above FEP preferably contains 0.1 to 10 mol% monomer units derived from monomers copolymerizable with TFE and HFP (a copolymer in which TFE units and HFP units total 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0039] Monomers copolymerizable with TFE and HFP include PAVE, monomers represented by formula (X), and alkyl perfluorovinyl ether derivatives represented by formula (II). Furthermore, monomers copolymerizable with TFE and HFP include unsaturated monocarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride, as well as unsaturated dicarboxylic acids and acid anhydrides of unsaturated dicarboxylic acids.

[0040] The melting point of FEP is preferably 150 to less than 324°C, more preferably 200 to 320°C, and even more preferably 240 to 320°C.

[0041] As for ETFE, copolymers in which the molar ratio of TFE units to ethylene units (TFE units / ethylene units) is 20 / 80 or more and 90 / 10 or less are preferred. A more preferred molar ratio is 37 / 63 or more and 85 / 15 or less, and an even more preferred molar ratio is 38 / 62 or more and 80 / 20 or less. ETFE may also be a copolymer consisting of TFE, ethylene, and monomers copolymerizable with TFE and ethylene. The above ETFE preferably contains 0.1 to 10 mol% monomer units derived from monomers copolymerizable with TFE and ethylene (a copolymer in which the total of TFE units and ethylene units is 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0042] Monomers copolymerizable with TFE and ethylene include the following formula CH2=CX 1 Rf 2 CF2=CFRf 2 CF2 = CFORf 2 CH2=C(Rf 2 )2(where, X 1 is a hydrogen atom or a fluorine atom, Rf 2 represents a fluoroalkyl group which may contain an ether bond. Examples include monomers represented by ) and monomers represented by formula (X), among which CF2=CFRf 2 CF2 = CFORf 2 and CH2=CX 1 Rf 2 A fluorine-containing vinyl monomer represented by formula (X) is preferred, and HFP, CF2=CF-ORf 3 (In the formula, Rf 3 ) represents a perfluoroalkyl group with 1 to 5 carbon atoms. Perfluoro(alkyl vinyl ether), represented as CF2=CF-CF2-O-Rf 4 (In the formula, Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) represents perfluoroalkyl allyl ethers and Rf 2 CH2=CX is a fluoroalkyl group with 1 to 8 carbon atoms. 1 Rf 2 More preferably, a fluorine-containing vinyl monomer represented by is preferred. Other monomers copolymerizable with TFE and ethylene include unsaturated monocarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride, as well as unsaturated dicarboxylic acids and acid anhydrides of unsaturated dicarboxylic acids.

[0043] ETFE preferably has a melting point of 140 to less than 324°C, more preferably 160 to 320°C, and even more preferably 195 to 320°C.

[0044] The content of each monomer unit of the polymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0045] The thermal decomposition temperature of fluororesin A is preferably 330°C or higher, more preferably 350°C or higher, even more preferably 370°C or higher, and also preferably 500°C or lower, more preferably 480°C or lower, and even more preferably 470°C or lower.

[0046] The thermal decomposition temperature of fluororesin A was measured using a STA7200 thermal analyzer manufactured by Hitachi High-Tech Science Corporation. The measurement was performed under a nitrogen purge atmosphere of 200 mL / min. 10 mg of the sample was placed in an aluminum pan, held at 25°C for 10 minutes, and then heated to 600°C at a heating rate of 10°C / min. The thermal decomposition temperature was defined as the temperature at which the initial mass decreased by 5% (Td5). Furthermore, in the case where fluororesin A has been reduced in molecular weight by irradiation with ionizing radiation, the thermal decomposition temperature was measured after irradiation with ionizing radiation and subsequent degassing.

[0047] Fluororesin A has a main chain with 10 carbon atoms. 6 Each molecule may have 100 to 2000 unstable end groups. The unstable end groups are -COF and -COOH, and the above numbers represent the total number of these groups.

[0048] The number of unstable end groups can be measured by infrared spectroscopy. Specifically, first, a film with a thickness of 0.25 to 0.3 mm is produced by melt extrusion molding of fluororesin A. This film is analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of fluororesin A, and a difference spectrum is obtained from this spectrum and the base spectrum, which is completely fluorinated and does not contain unstable end groups. From the absorption peaks of specific unstable end groups that appear in this difference spectrum, the carbon content of fluororesin A is calculated according to the following formula (A). 6 Calculate the number of unstable terminals N per unit. N = I × K / t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)

[0049] In the composition disclosed herein, it is preferable that resin B forms a sea-island structure and fluororesin A forms islands.

[0050] In the compositions of this disclosure, the dispersion particle size of fluororesin A is preferably 5.0 μm or less, more preferably 4.0 μm or less, and even more preferably 2.0 μm or less. The lower limit is not particularly limited, but 0.1 μm or more is preferred.

[0051] The particle size of the dispersed fluororesin A is determined according to the following procedure. First, a test specimen is obtained by cutting the composition perpendicular to its longitudinal direction, and its cross-section is observed with a confocal laser microscope. The obtained microscope image is analyzed using image analysis software (Image J) to determine the equivalent circle diameter of the dispersed phase. Then, the equivalent circle diameters for 20 dispersed phases are calculated, and the average of these is taken as the dispersed particle diameter.

[0052] Resin B is not particularly limited as long as it has a melt flow rate of 30 g / 10 min or more at a melting point of +8°C, but liquid crystal polymers, polyetherimides, polyphenylene sulfide, polyarylether ketones, polysulfones, polyethersulfones, etc. can be used. Among these, at least one selected from the group consisting of liquid crystal polymers, polyetherimides, polyphenylene sulfide, polyarylether ketones, polysulfones, and polyethersulfones is preferred, and liquid crystal polymers are particularly preferred.

[0053] The liquid crystal polymer is not particularly limited, but it may be a polymer with a liquid crystal temperature (i.e., melting point) of 180°C to 380°C, and a thermotropic liquid crystal polymer that becomes a liquid crystal state such as a nematic when heated is preferred, for example, Type I liquid crystal polymers (such as biphenol / benzoic acid / parahydroxybenzoic acid (POB) copolymers) Type II liquid crystal polymers (such as hydroxynaphthoate (HNA) / POB copolymers) Type III liquid crystal polymers (such as POB / ethylene terephthalate copolymers) These are some examples. In particular, from the viewpoint of mixing temperature and liquid crystal transition temperature, at least one selected from the group consisting of type I liquid crystal polymers and type II liquid crystal polymers is preferred, and type II liquid crystal polymers are more preferred.

[0054] The melting point of the liquid crystal polymer is preferably 280°C or higher, more preferably 310°C or higher, and also preferably 380°C or lower, more preferably 350°C or lower.

[0055] As polyetherimides, for example, those having imide bonds and ether bonds within the molecule can be used.

[0056] The glass transition temperature of polyetherimide is preferably 180°C or higher, more preferably 200°C or higher, and also preferably 300°C or lower, more preferably 280°C or lower.

[0057] As the polyphenylene sulfide, for example, a resin having structural units represented by the following formula can be used. The proportion of these structural units is preferably 70 mol% or more. -(Ph-S)- In the formula, Ph represents a phenylene group, and examples of such phenylene groups include p-phenylene, m-phenylene, o-phenylene, alkyl-substituted phenylene, phenyl-substituted phenylene, halogen-substituted phenylene, amino-substituted phenylene, amide-substituted phenylene, p,p'-diphenylene sulfone, p,p'-biphenylene, and p,p'-biphenylene ether. Among these, p-phenylene is preferred.

[0058] The melting point of polyphenylene sulfide is preferably 240°C or higher, more preferably 270°C or higher, and also preferably 380°C or lower, more preferably 350°C or lower.

[0059] Examples of polyaryl ether ketones include polyether ketone (PEK), polyether ether ketone (PEEK), and polyether ketone ketone (PEKK). Among these, PEEK is preferred.

[0060] The melting point of the polyaryletherketone is preferably 320°C or higher, more preferably 340°C or higher, and also preferably 400°C or lower, more preferably 380°C or lower.

[0061] There are no particular restrictions on the type of polysulfone (polysulfone) used; any common type can be used.

[0062] The glass transition temperature of polysulfone is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 220°C or higher, and also preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.

[0063] There are no particular restrictions on the type of polyethersulfone (polyethersulfone) used; any common type can be used.

[0064] The glass transition temperature of polyethersulfone is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 220°C or higher, and also preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.

[0065] The melting points of liquid crystal polymers, polyetherimides, polyphenylene sulfides, and polyaryletherketones are the temperatures corresponding to the maximum values ​​in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC). The glass transition temperatures of polyetherimide, polysulfone, and polyethersulfone can be determined using a differential scanning calorimeter (Mettler-Toledo, DSC822e). A DSC curve is obtained by heating 10 mg of the sample at 10°C / min, and the temperature is found at the midpoint of the intersection of the baseline extensions of the DSC curve before and after the second-order transition and the tangent line at the inflection point of the DSC curve.

[0066] The thermal decomposition temperature of resin B is preferably 330°C or higher, more preferably 350°C or higher, and also preferably 600°C or lower, more preferably 550°C or lower.

[0067] The thermal decomposition temperature of resin B was measured using a Hitachi High-Tech Science Corporation STA7200 thermal analyzer. The measurement was performed under a nitrogen purge atmosphere of 200 mL / min. 10 mg of the sample was placed in an aluminum pan, held at 25°C for 10 minutes, and then heated to 600°C at a heating rate of 10°C / min. The thermal decomposition temperature was defined as the temperature at which the initial mass decreased by 5% (Td5).

[0068] In the compositions of this disclosure, the MFR of fluororesin A / MFR of resin B may be 0.2 to 10, but from the viewpoint of affinity between fluororesin A and resin B, it is preferably 0.3 or more, more preferably 0.5 or more, and also preferably 5 or less, more preferably 3 or less.

[0069] When calculating the MFR of fluororesin A and resin B, the MFR of each resin is measured at the same temperature. The measurement temperature is close to the mixing temperature (molding temperature of resin B) when fluororesin A and resin B are mixed, specifically 325°C. The MFR of each resin is obtained according to ASTM D1238, using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) as the mass of polymer flowing out of a nozzle with an inner diameter of 2 mm and a length of 8 mm per 10 minutes under a load of 2.16 kg at 325 °C (g / 10 min).

[0070] The MFR of fluororesin A at 325°C is not particularly limited as long as the above relationship is satisfied, but is preferably 30 g / 10 min or more, more preferably 50 g / 10 min or more, even more preferably 100 g / 10 min or more, and also preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, and even more preferably 500 g / 10 min or less. Similarly, the MFR of resin B at 325°C is not particularly limited as long as it satisfies the above relationship, but is preferably 30 g / 10 min or more, more preferably 50 g / 10 min or more, even more preferably 100 g / 10 min or more, and also preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, and even more preferably 500 g / 10 min or less.

[0071] The MFR at the melting point of resin B + 8°C should be 30 g / 10 min or more, preferably 40 g / 10 min or more, more preferably 60 g / 10 min or more, and also preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, and even more preferably 700 g / 10 min or less.

[0072] The MFR of resin B at 8°C was measured using the same method as the MFR at 325°C, except for the difference in measurement temperature.

[0073] In the compositions of this disclosure, the content of fluororesin A is preferably 10% by volume or more, more preferably 20% by volume or more, even more preferably 25% by volume or more, and also preferably 45% by volume or less, more preferably 40% by volume or less, and even more preferably 35% by volume or less.

[0074] In the compositions of this disclosure, the content of resin B is preferably 55% by volume or more, more preferably 60% by volume or more, even more preferably 65% ​​by volume or more, and also preferably 90% by volume or less, more preferably 80% by volume or less, and even more preferably 75% by volume or less.

[0075] In the compositions of this disclosure, the total content of fluororesin A and resin B is preferably 70% by volume or more, more preferably 80% by volume or more, and even more preferably 90% by volume or more. The upper limit is not particularly limited and may be 100% by volume.

[0076] In the compositions of this disclosure, the volume ratio of fluororesin A to resin B (fluororesin A / resin B) is preferably 10 / 90 or more, more preferably 20 / 80 or more, even more preferably 25 / 75 or more, and also preferably 45 / 55 or less, more preferably 40 / 60 or less, and even more preferably 35 / 65 or less.

[0077] The compositions of this disclosure may include fluororesin C that does not correspond to fluororesin A. Fluororesin C is not particularly limited as long as it does not satisfy the MFR of fluororesin C / MFR of resin B = 0.2 to 10. When calculating the MFR of fluororesin C and resin B, the MFR of each resin is measured using the same method as when calculating the MFR of fluororesin A and resin B.

[0078] Furthermore, the aforementioned fluororesins A, B, and C may be used individually or in combination of two or more types.

[0079] The compositions of this disclosure may further include additives.

[0080] As additives, epoxy compounds, amine compounds, oxazoline compounds, acid anhydrides, etc., can be used. Among these, oxazoline compounds are preferred.

[0081] The oxazoline compound is not particularly limited as long as it has one or more oxazoline groups, but it is preferable to have two or more oxazoline groups, and more preferably to have two oxazoline groups. Specific examples of oxazoline compounds having two oxazoline groups include 1,3-bis(4,5-dihydro-2-oxazolyl)benzene [1,3-PBO] and its isomer 1,4-PBO. Furthermore, the oxazoline compound may also be an oligomer or polymer having an oxazoline group. Specific examples of polymers having an oxazoline group include poly-2-vinyl-2-oxazoline [Pvozo].

[0082] Fillers can also be used as additives. Specific examples of fillers include inorganic compounds such as silica (more specifically crystalline silica, fused silica, spherical fused silica, etc.), titanium dioxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate, potassium titanate, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO); minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite; carbon compounds such as carbon black, acetylene black, Ketjenblack, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and various types of glass such as glass beads, glass flakes, and glass balloons.

[0083] In addition to those described above, other common additives used in resins, such as crosslinking agents, antistatic agents, heat stabilizers, foaming agents, foaming nucleating agents, antioxidants, surfactants, photopolymerization initiators, anti-wear agents, and surface modifiers, can also be used as additives. Furthermore, resins other than fluororesin A and resin B may be used as additives.

[0084] In the compositions of this disclosure, the content of additives is preferably 0.1% by volume or more, more preferably 1% by volume or more, even more preferably 3% by volume or more, and also preferably 15% by volume or less, more preferably 12% by volume or less, and even more preferably 10% by volume or less.

[0085] <Molded body of this disclosure> The molded articles of this disclosure include the compositions of this disclosure.

[0086] The molded articles of this disclosure are obtained by molding the compositions of this disclosure. The molding method is not particularly limited, and conventional methods such as injection molding, blow molding, inflation molding, and vacuum / pressure molding can be used.

[0087] The molded articles of this disclosure are suitably used as dielectric materials, particularly low-dielectric substrate materials (e.g., insulating materials). In this specification, "low dielectric substrate material" means a material having a relative permittivity of 5.0 or less at 25°C and 10GHz, and a dielectric loss tangent of 0.003 or less at 25°C and 10GHz. A material having a relative permittivity of 4.0 or less at 25°C and 10GHz, and a dielectric loss tangent of 0.002 or less at 25°C and 10GHz is more preferred, and a material having a relative permittivity of 3.5 or less at 25°C and 10GHz, and a dielectric loss tangent of 0.0012 or less at 25°C and 10GHz is even more preferred.

[0088] When the molded article of this disclosure is used as a dielectric material, there are no particular limitations on its application. For example, electrical and electronic components such as connectors, sockets, relay components, coil bobbins, optical pickups, oscillators, printed circuit boards, and computer-related components; semiconductor manufacturing process-related components such as IC trays and wafer carriers; household electrical appliance components such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture components such as lamp reflectors and lamp holders; audio product components such as compact discs and speakers; communication equipment components such as ferrules for optical cables, telephone components, facsimile components, and modems; copier-related components such as separation claws and heater holders; and impellers. It can be used in a wide range of applications, including mechanical parts such as fans, gears, bearings, motor parts and cases, automotive mechanical parts, engine parts, engine compartment parts, electrical parts, interior parts, cooking utensils such as microwave cooking pots and heat-resistant tableware, thermal insulation and soundproofing materials such as flooring and wall materials, building materials such as beams and columns, roofing materials, or civil engineering and construction materials, aircraft, spacecraft and space equipment parts, radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical instrument parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, and sanitary fixtures.

[0089] <Laminate of this disclosure> The laminate of the present disclosure includes a metal foil and a molded body of the present disclosure.

[0090] Examples of metals used for metal foil include aluminum, iron, silver, gold, and ruthenium. Alloys of these metals can also be used. Among these, copper is preferred. Rolled copper, electrolytic copper, and other types of copper can be used.

[0091] The thickness of the laminate according to this disclosure is preferably 10 μm to 1000 μm. Furthermore, in the laminate according to this disclosure, the thickness of the molded article according to this disclosure is preferably 1 μm to 100 μm. In addition, the laminates and molded articles of this disclosure are preferably in the form of sheets with substantially constant thickness. However, if there are parts with different thicknesses, the thickness of the points divided into 10 equal intervals in the longitudinal direction is measured and averaged.

[0092] The laminate of this disclosure may have other layers laminated in addition to the metal foil and the molded body of this disclosure described above.

[0093] The laminate of this disclosure is suitably used as a circuit board, particularly as a printed circuit board, a multilayer circuit board (multilayer substrate), and a high-frequency circuit board.

[0094] A high-frequency circuit board is a circuit board capable of operating in the high-frequency band. The high-frequency band may be 1 GHz or higher, preferably 3 GHz or higher, and more preferably 5 GHz or higher. There is no particular upper limit, but it may be 100 GHz or lower.

[0095] <Manufacturing method of this disclosure> The manufacturing method of the present disclosure involves an MFR adjustment step in which the ratio of (MFR of fluororesin A) / (MFR of resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 min or more at a melting point of +8°C) is adjusted to 0.2 to 10, thereby obtaining a composition containing fluororesin A and resin B.

[0096] Fluororesins A and B can be the same as those used in the compositions of this disclosure described above.

[0097] In the MFR adjustment process, the MFR of any of the resins may be adjusted, but it is preferable to adjust the MFR of at least the fluororesin to obtain fluororesin A that satisfies the ratio of the MFR of fluororesin A to the MFR of resin B = 0.2 to 10. Furthermore, while the method for adjusting the MFR is not particularly limited, it is preferable to adjust the molecular weight of the resin. Methods for adjusting the molecular weight of the resin include employing a polymerization method that lowers the molecular weight of the resin, reducing the molecular weight of the resin by shearing during kneading, and reducing the molecular weight of the resin by irradiating with ionizing radiation. In other words, in the MFR adjustment process, it is preferable to obtain fluororesin A by polymerization, kneading, or irradiation with ionizing radiation.

[0098] The polymerization method used to lower the molecular weight of the resin is not particularly limited; the materials and reaction conditions should be appropriately set according to the desired molecular weight.

[0099] When reducing the molecular weight of the resin by shearing during mixing, the shearing rate should be 100 seconds. -1 It is preferable to set it to ( / sec) or more. The upper limit is not particularly limited, but for example, 5000 seconds. -1 It is less than ( / sec). The shear rate (γ) is a value that can be calculated, for example, using the following formula. γ = πDr / C D: Screw outer diameter (mm) r: Screw rotation speed (rpm) C: Tip clearance (mm)

[0100] Ionizing radiation is radiation that causes ionization in matter, and is classified into particle beams and electromagnetic waves. Particle beams are further classified into charged particle beams such as alpha rays and beta rays, and uncharged particle beams such as neutron beams. Examples of electromagnetic waves include X-rays and gamma rays. Ionizing radiation can also be classified into direct ionizing radiation and indirect ionizing radiation. In this case, charged particle beams fall under direct ionizing radiation, while uncharged particle beams and electromagnetic waves fall under indirect ionizing radiation. In terms of energy penetrating the entire resin, indirect ionizing radiation is preferred, electromagnetic waves are more preferred, and gamma rays are even more preferred.

[0101] The fluororesin irradiated with ionizing radiation is preferably a fluororesin that can be melt-processed. In this specification, "melt-processable" means that the polymer can be melted and processed using conventional processing equipment such as extruders and injection molding machines.

[0102] Examples of fluororesins that can be melt-processed include the aforementioned PFA, FEP, ETFE, EFEP, PCTFE, PVdF, etc., and from the viewpoint of affinity with resin B, at least one selected from the group consisting of PFA and FEP is preferred, with FEP being more preferred.

[0103] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0104] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0105] The materials used in the examples are as follows: (Fluororesin) (Note that in the following examples, FEP(2) and (3) correspond to fluororesin A.) FEP(1) (TFE units / HFP units (molar ratio) = 88.0 / 12.0, MFR (325℃): 5.6g / 10min, thermal decomposition temperature: 427℃) FEP(2) (Synthesized using the method described below; TFE units / HFP units / PPVE units (molar ratio) = 90.9:8.80:0.35; MFR (325℃): 228.0g / 10; Thermal decomposition temperature: 470℃) FEP(3) (Synthesized using the method described below; TFE units / HFP units (molar ratio) = 88.0 / 12.0; MFR (325℃): 270.2g / 10; Thermal decomposition temperature: 463℃) (Resin B) LCP(1) (Type II liquid crystal polymer, melting point: 313°C, MFR (325°C): 206.5g / 10min, MFR (321°C (melting point + 8°C)): 62.4g / 10min, thermal decomposition temperature: 501°C) LCP(2) (Type II liquid crystal polymer, melting point: 322°C, MFR (325°C): 206.7g / 10min, MFR (330°C (melting point + 8°C)): 648.4g / 10min, thermal decomposition temperature: 501°C)

[0106] Method for synthesizing FEP(2) 1100g of deoxygenated, deionized water was placed in a 4L glass-lined autoclave, the autoclave was evacuated, and 1100g of hexafluoropropylene (HFP) was added, maintaining the internal temperature at 28°C. Next, 8.0g of perfluoropropyl vinyl ether (PPVE) and 5.0g of methanol were charged into the autoclave, and tetrafluoroethylene (TFE) was injected under pressure to 0.89 MPaG while stirring. Then, 8.0g of di-iso-propyl peroxydicarbonate was charged to start polymerization. As the pressure decreased during polymerization, additional tetrafluoroethylene was injected under pressure to maintain the polymerization pressure at 0.89 MPaG, and polymerization was carried out for 10.6 hours. After polymerization was complete, the remaining monomer and solvent were recovered, and the product was washed and dried to obtain 74g of polymerization powder.

[0107] Method for synthesizing FEP(3) An aluminum zip-lock bag containing 1000g of FEP pellets was placed on a conveyor belt and irradiated with 500kGy of gamma rays while moving around the radiation source. Afterwards, the bag was degassed at 200°C for 4 hours to obtain the sample.

[0108] Examples, Comparative Examples The mixing of 13.72 g of resin B and 9.03 g of fluororesin was investigated using a circulating twin-screw extruder (Xplore MC15HT: manufactured by Xplore Instruments) under the conditions shown in Table 1. The materials were pre-dry blended before being added from the hopper and mixed for 5 minutes at 500 rpm. The mixing temperature was as specified in Table 1. After mixing, samples were taken as strands. The cross-sections of the obtained strands were observed with a laser microscope to evaluate the morphology (resin dispersion state) after kneading. In both cases, resin B formed a sea-island structure with fluororesin forming islands. However, the example showed smaller dispersed particle sizes of the islands (fluororesin) and a better dispersion state compared to the comparative example. The appearance of the strands was also good. The evaluation criteria for the appearance of the strand are as follows: A: No roughness or aggregation is observed on the strand surface. B: Roughness and aggregation are observed on the strand surface.

[0109] [Table 1]

Claims

1. The material comprises fluororesin A and resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 min or more under a melting point of +8°C and a load of 2.16 kg. The fluororesin A is a resin that satisfies the condition that the MFR of fluororesin A under a 325°C × 2.16 kg load / the MFR of resin B under a 325°C × 2.16 kg load = 0.2 to 10. The volume ratio of fluororesin A to resin B (fluororesin A / resin B) is 45 / 55 or less. A composition in which the resin B is a liquid crystal polymer.

2. The composition according to claim 1, wherein the MFR of the fluororesin A under a load of 325°C × 2.16 kg is 30 g / 10 min or more.

3. The composition according to claim 1 or 2, wherein the fluororesin A is at least one selected from the group consisting of tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer and tetrafluoroethylene / hexafluoropropylene copolymer.

4. The composition according to claim 1 or 2, wherein the content of the fluororesin A is 10% by volume or more.

5. The composition according to claim 1 or 2, wherein the dispersed particle size of the fluororesin A is 5.0 μm or less.

6. The composition according to claim 1 or 2, comprising an additive.

7. A molded article comprising the composition according to claim 1 or 2.

8. A molded article according to claim 7, used in low dielectric substrate materials.

9. A laminate comprising a metal foil and the molded body described in claim 8.

10. The laminate according to claim 9, wherein the metal foil is made of copper.

11. A method for producing a composition to obtain a composition containing fluororesin A and resin B, through an MFR adjustment step of adjusting (MFR of fluororesin A at 325°C × 2.16 kg load) / (MFR of resin B (excluding fluororesin A) at 325°C × 2.16 kg load, where the melt flow rate at melting point + 8°C × 2.16 kg load is 30 g / 10 min or more) to 0.2 to 10, The volume ratio of fluororesin A to resin B (fluororesin A / resin B) is 45 / 55 or less. A method for producing a composition in which the resin B is a liquid crystal polymer.

12. The method for producing the composition according to claim 11, wherein the fluororesin A is obtained by polymerization, kneading, or irradiation with ionizing radiation in the MFR adjustment step.

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