Composition, molded article, laminate, and method for producing composition

Abstract

The purpose of the present invention is to provide a composition, a molded body, a laminate, and a method for producing the composition, whereby aggregation of a fluororesin, which causes a poor appearance of a wire material, can be suppressed even when the proportion of the fluororesin increases. The present disclosure relates to a composition containing a fluororesin A and a resin B having a melt flow rate at a melting point + 8 DEG C of 30 g / 10 minutes or more (excluding the fluororesin A), the fluororesin A satisfying the MFR of the fluororesin A / MFR of the resin B = 0.2-10.

Description

Technical Field

[0001] The present disclosure relates to a composition, a molded body, a laminate, and a method for producing the composition. Background Art

[0002] Various studies have been conducted on compositions containing fluororesins and liquid crystal polymers (for example, refer to Patent Documents 1 to 3).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2001-187833

[0006] Patent Document 2: Japanese Patent Application Publication No. 2018-177931

[0007] Patent Document 3: Japanese Patent Application Publication No. 2019-065061 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present inventors have conducted research and found that, as in the examples of Patent Documents 2 and 3, when the proportion of fluororesin is increased, the affinity between the liquid crystal polymer and the fluororesin decreases, and the fluororesin is easily aggregated (poor dispersion). Aggregation of the fluororesin leads to poor appearance of the strands, so it is preferable to prevent aggregation of the fluororesin as much as possible.

[0010] An object of the present disclosure is to provide a composition, a molded product, a laminate, and a method for producing the composition, which can suppress the aggregation of the fluororesin which causes poor strand appearance even when the proportion of the fluororesin is increased.

[0011] Means for solving problems

[0012] The present disclosure (1) is a composition (hereinafter also referred to as "the composition of the present disclosure") comprising 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 of +8°C.

[0013] The fluororesin A is a resin satisfying the relationship of MFR of the fluororesin A / MFR of the resin B=0.2-10.

[0014] 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.

[0015] The present disclosure (3) is the composition described in the present disclosure (1) or (2), wherein the fluororesin A is at least one selected from the group consisting of tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.

[0016] 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 liquid crystal polymers, polyetherimides, polyphenylene sulfides, polyaryletherketones, polysulfones, and polyethersulfones.

[0017] 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.

[0018] The present disclosure (6) is the composition according to any one of the present disclosures (1) to (5), wherein the dispersed particle size of the fluororesin A is 5.0 μm or less.

[0019] The present disclosure (7) is the composition according to any one of the present disclosures (1) to (6), which contains an additive.

[0020] The present disclosure (8) is a molded product (hereinafter also referred to as “a molded product of the present disclosure”) comprising the composition according to any one of the present disclosures (1) to (7).

[0021] The present disclosure (9) is the molded product described in the present disclosure (8), which is used for a low dielectric substrate material.

[0022] The present disclosure (10) is a laminate (hereinafter also referred to as "laminated body of the present disclosure") comprising a metal foil and the molded body described in the present disclosure (8) or (9).

[0023] The present disclosure (11) is the laminate according to the present disclosure (10), wherein the metal foil is copper.

[0024] The present disclosure (12) is a method for producing a composition (hereinafter also referred to as "the production method of the present disclosure"), in which a composition comprising the above-mentioned fluororesin A and the above-mentioned resin B is obtained through an MFR adjustment step of adjusting (MFR of fluororesin A) / (MFR of resin B) to 0.2 to 10, wherein the above-mentioned resin B does not include the above-mentioned fluororesin A and has a melt flow rate of 30 g / 10 minutes or more at a melting point of +8°C.

[0025] The present disclosure (13) is a method for producing the composition according to the present disclosure (12), wherein in the MFR adjustment step, the fluororesin A is obtained by polymerization, kneading or irradiation with ionizing radiation.

[0026] Effects of the Invention

[0027] According to the present invention, there can be provided a composition, a molded product, a laminate, and a method for producing the composition, which can suppress the aggregation of the fluororesin which causes poor strand appearance even when the proportion of the fluororesin is increased. DETAILED DESCRIPTION

[0028] In the present specification, the "organic group" refers to a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0029] Examples of the "organic group" include:

[0030] an alkyl group 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, a cyano group,

[0031] Formyl,

[0032] RaO-,

[0033] RaCO-,

[0034] RaSO2-,

[0035] RaCOO-

[0036] RaNRaCO-,

[0037] RaCONRa-

[0038] RaOCO-,

[0039] RaOSO2-, and

[0040] RaNRbSO2-

[0041] (In these formulas, Ra is independently an alkyl group 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,

[0042] an aryl group which may have one or more substituents,

[0043] an aralkyl group which may have one or more substituents,

[0044] A non-aromatic heterocyclic group which may have one or more substituents, or

[0045] a heteroaryl group which may have one or more substituents,

[0046] Rb is independently H or an alkyl group which may have one or more substituents).

[0047] As the organic group, an alkyl group which may have one or more substituents is preferred.

[0048] Hereinafter, the present disclosure will be described in detail.

[0049] <Composition of the present disclosure>

[0050] The composition of the present invention comprises fluororesin A and resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 min or more at melting point + 8°C, wherein fluororesin A is a resin having MFR of fluororesin A / MFR of resin B satisfying 0.2 to 10.

[0051] According to the composition of the present disclosure, by adjusting the MFR of fluororesin A / MFR of resin B to the above range, the affinity between fluororesin A and resin B can be improved. As a result, even when the proportion of fluororesin is increased, aggregation of fluororesin which causes poor strand appearance can be suppressed.

[0052] Examples of the fluororesin A include tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymers [PFA], TFE / hexafluoropropylene [HFP] copolymers [FEP], ethylene [Et] / TFE copolymers [ETFE], Et / TFE / HFP copolymers [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymers, CTFE / TFE / PAVE copolymers, Et / CTFE copolymers, polyvinyl fluoride [PVF], polyvinylidene fluoride [PVdF], vinylidene fluoride [VdF] / TFE copolymers, VdF / HFP copolymers, VdF / TFE / HFP copolymers, VdF / HFP / (meth)acrylic acid copolymers, VdF / CTFE copolymers, VdF / pentafluoropropylene copolymers, VdF / PAVE / TFE copolymers, and TFE / perfluoroalkyl allyl ether copolymers. Perfluoroalkyl allyl ethers are CF2=CFCF2-O-Rf 4 (Rf 4 A monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms).

[0053] The fluororesin A is preferably 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], and more preferably FEP, from the viewpoint of affinity with the resin B.

[0054] The perfluorovinyl ether is not particularly limited, and examples thereof include the following general formula (1):

[0055] CF2=CF-ORf (1)

[0056] (wherein Rf represents a perfluoro organic group) and the like. In the present specification, the above-mentioned "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0057] Examples of perfluorovinyl ethers include perfluoro(alkyl vinyl ether) [PAVE] in which Rf in the general formula (1) represents a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

[0058] Examples of the perfluoroalkyl group in PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl. Preferably, the perfluoroalkyl group is perfluoro(propyl vinyl ether) [PPVE] in which the perfluoroalkyl group is perfluoropropyl.

[0059] As the perfluorovinyl ether, further examples include those in which Rf in the general formula (1) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:

[0060] [Chemistry 1]

[0061]

[0062] (wherein m represents 0 or an integer of 1 to 4) and Rf is the following formula:

[0063] [Chemistry 2]

[0064]

[0065] (wherein n represents an integer of 1 to 4) and the like.

[0066] The (perfluoroalkyl)ethylene is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene [PFHE], and (perfluorooctyl)ethylene.

[0067] PFA is not particularly limited, but preferably the molar ratio of TFE unit to PAVE unit (TFE unit / PAVE unit) is 70 / 30 or more and less than 99 / 1. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and a further preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above-mentioned PFA preferably contains 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and PAVE (a copolymer in which the total of TFE unit and PAVE unit is 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0068] Examples of 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, representing a hydrogen atom or a fluorine atom, Z 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10. ) and a vinyl monomer represented by formula (II): CF2=CF-OCH2-Rf 1 (Where Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) represents an alkyl perfluorovinyl ether derivative, 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 are the same or different, representing a hydrogen atom, a chlorine atom or a fluorine atom, Z 8 and Z 9 represents a hydrogen atom or a fluorine atom, Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) and the like. As the allyl ether monomer, preferably, CH2=CFCF2-O-Rf 4 CF2=CFCF2-O-Rf 4 (perfluoroalkyl allyl ether), CF2=CFCH2-O-Rf 4 、CH2=CHCF2-O-Rf 4 (Where Rf 4 The same as in the above formula (X) etc.

[0069] Examples of monomers copolymerizable with TFE and PAVE include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and anhydrides of unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0070] The melting point of PFA is preferably 180 to less than 324°C, more preferably 230 to 320°C, and further preferably 280 to 320°C.

[0071] There are no particular restrictions on the FEP, but preferably the copolymer has a molar ratio of TFE unit to HFP unit (TFE unit / HFP unit) of 70 / 30 or more and less than 99 / 1. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and a further preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above-mentioned FEP preferably contains 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP (a copolymer having a total of 90 to 99.9 mol% of TFE unit and HFP unit), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0072] Examples of monomers copolymerizable with TFE and HFP include PAVE, monomers represented by formula (X), alkyl perfluorovinyl ether derivatives represented by formula (II), etc. Examples of monomers copolymerizable with TFE and HFP include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and anhydrides of unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0073] The melting point of FEP is preferably 150°C to less than 324°C, more preferably 200 to 320°C, and further preferably 240 to 320°C.

[0074] As ETFE, preferably the molar ratio of TFE unit to ethylene unit (TFE unit / ethylene unit) is 20 / 80 or more and 90 / 10 or less. A more preferred molar ratio is 37 / 63 or more and 85 / 15 or less, and a further preferred molar ratio is 38 / 62 or more and 80 / 20 or less. ETFE can be a copolymer consisting of TFE, ethylene and a monomer copolymerizable with TFE and ethylene. The monomer unit of the above-mentioned ETFE preferably comes from a monomer copolymerizable with TFE and ethylene, which is 0.1 to 10 mol% (a copolymer in which the TFE unit and the ethylene unit add up to 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0075] As monomers copolymerizable with TFE and ethylene, the following are mentioned:

[0076] CH2=CX 1R 2 CF2=CFRf 2 CF2=CFORf 2 、CH2=C(Rf 2 )2(where X 1 represents a hydrogen atom or a fluorine atom, Rf 2 represents a fluorinated alkyl group which may contain an ether bond. ) represented by a monomer, a monomer represented by formula (X), among which CF2=CFRf is preferred. 2 CF2=CFORf 2 and CH2=CX 1 R 2 The fluorine-containing vinyl monomer represented by formula (X), more preferably HFP, CF2=CF-ORf 3 (Where Rf 3 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) represents a perfluoro(alkyl vinyl ether), CF2=CF-CF2-O-Rf 4 (Where Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) represents a perfluoroalkyl allyl ether and Rf 2 CH2=CX is a fluoroalkyl group having 1 to 8 carbon atoms 1 R 2 In addition, examples of monomers copolymerizable with TFE and ethylene include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and anhydrides of unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0077] The melting point of ETFE is preferably 140°C to less than 324°C, more preferably 160 to 320°C, and further preferably 195 to 320°C.

[0078] The content of each monomer unit of the above polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis according to the kind of monomer.

[0079] The thermal decomposition temperature of the fluororesin A is preferably 330°C or higher, more preferably 350°C or higher, further preferably 370°C or higher, and is preferably 500°C or lower, more preferably 480°C or lower, further preferably 470°C or lower.

[0080] It should be noted that the thermal decomposition temperature of fluororesin A was measured using a thermal analyzer STA7200 manufactured by Hitachi High-Tech Science. The measurement was performed under a nitrogen purge atmosphere of 200 mL / min. 10 mg of the sample was placed in an aluminum pan, kept at 25°C for 10 minutes, and then heated to 600°C at a heating rate of 10°C / min. The temperature (Td5) at which the initial mass was reduced by 5% was taken as the thermal decomposition temperature.

[0081] When the molecular weight of the fluororesin A is reduced by irradiation with ionizing radiation, the thermal decomposition temperature is measured after degassing operation is performed after irradiation with ionizing radiation.

[0082] Fluororesin A per 10 6 The number of carbon atoms in the main chain can be 100 to 2000 unstable terminal groups. The unstable terminal groups are -COF and -COOH, and the above number is their total number.

[0083] It should be noted that the number of unstable terminal groups can be determined by infrared spectroscopy. Specifically, first, fluororesin A is melt-extruded to form a film with a thickness of 0.25 to 0.3 mm. The film is analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of fluororesin A, and a differential spectrum with the background spectrum of a completely fluorinated material without the presence of unstable terminal groups is obtained. From the absorption peak of the specific unstable terminal group that appears in the differential spectrum, the number of unstable terminal groups per 10 in fluororesin A is calculated according to the following formula (A). 6 The number N of unstable terminal groups of a carbon source.

[0084] N=I×K / t(A)

[0085] I: Absorbance

[0086] K: Correction coefficient

[0087] t: film thickness (mm)

[0088] The composition of the present disclosure preferably forms a sea-island structure in which the resin B serves as the sea and the fluororesin A serves as the islands.

[0089] In the composition of the present disclosure, the dispersed particle size of the fluororesin A is preferably 5.0 μm or less, more preferably 4.0 μm or less, and further preferably 2.0 μm or less. The lower limit is not particularly limited, but is preferably 0.1 μm or more.

[0090] It should be noted that the dispersed particle size of the fluororesin A is determined according to the following procedure.

[0091] First, the composition was cut perpendicularly to the length direction to obtain a test piece, and its cross section was observed using a confocal laser microscope. The obtained microscope image was analyzed using image analysis software (Image J) to obtain the equivalent circular diameter of the dispersed phase. Then, the equivalent circular diameters of 20 dispersed phases were calculated, and the average value was used as the dispersed particle size.

[0092] As resin B, there is no particular limitation as long as the melt flow rate at melting point + 8°C is 30 g / 10 minutes or more, and liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryletherketone, polysulfone, polyethersulfone, etc. can be used. Among them, at least one selected from the group consisting of liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryletherketone, polysulfone and polyethersulfone is preferred, and liquid crystal polymer is particularly preferred.

[0093] The liquid crystal polymer is not particularly limited, and may be a polymer having a liquid crystalization temperature (i.e., melting point) of 180° C. to 380° C., preferably a thermotropic liquid crystal polymer that becomes a liquid crystal state such as a nematic state by heating, for example, the following liquid crystal polymers are preferred:

[0094] Type I liquid crystal polymers (biphenol / benzoic acid / parahydroxybenzoic acid (POB) copolymers, etc.),

[0095] Type II liquid crystal polymers (hydroxynaphthoic acid (HNA) / POB copolymers, etc.),

[0096] Type III liquid crystal polymer (POB / ethylene terephthalate copolymer, etc.).

[0097] Among them, from the viewpoint of kneading 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.

[0098] The melting point of the liquid crystal polymer is preferably 280° C. or higher, more preferably 310° C. or higher, and is preferably 380° C. or lower, more preferably 350° C. or lower.

[0099] As the polyetherimide, for example, a polyetherimide having an imide bond and an ether bond in the molecule can be used.

[0100] The glass transition temperature of the polyetherimide is preferably 180° C. or higher, more preferably 200° C. or higher, and is preferably 300° C. or lower, more preferably 280° C. or lower.

[0101] As polyphenylene sulfide, for example, a resin having a structural unit represented by the following formula can be used: The ratio of the structural unit is preferably 70 mol% or more.

[0102] -(Ph-S)-

[0103] Ph in the formula is a phenylene group, and examples of the phenylene group 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 them, p-phenylene is preferred.

[0104] The melting point of polyphenylene sulfide is preferably 240° C. or higher, more preferably 270° C. or higher, and is preferably 380° C. or lower, more preferably 350° C. or lower.

[0105] Examples of the polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), etc. Among them, PEEK is preferred.

[0106] The melting point of the polyaryletherketone is preferably 320°C or higher, more preferably 340°C or higher, and is preferably 400°C or lower, more preferably 380°C or lower.

[0107] The polysulfone (polysulfone) is not particularly limited, and general polysulfones can be used.

[0108] The glass transition temperature of polysulfone is preferably 180°C or higher, more preferably 200°C or higher, and further preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and further preferably 260°C or lower.

[0109] The polyethersulfone (polyethersulfone) is not particularly limited, and general polyethersulfone can be used.

[0110] The glass transition temperature of polyethersulfone is preferably 180°C or higher, more preferably 200°C or higher, and further preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and further preferably 260°C or lower.

[0111] The melting points of liquid crystal polymers, polyetherimides, polyphenylene sulfide and polyaryletherketones are temperatures corresponding to the maximum values ​​in the heat of solution curves when the temperature is increased at a rate of 10° C. / min using a differential scanning calorimeter (DSC).

[0112] The glass transition temperature of polyetherimide, polysulfone and polyethersulfone can be obtained as follows: a DSC curve is obtained by heating 10 mg of a sample at 10°C / min using a differential scanning calorimeter (DSC822e manufactured by Mettler Toredo), and the glass transition temperature is obtained as the temperature of the midpoint of the two intersections of the extended line of the baseline before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0113] The thermal decomposition temperature of the resin B is preferably 330° C. or higher, more preferably 350° C. or higher, and is preferably 600° C. or lower, more preferably 550° C. or lower.

[0114] It should be noted that the thermal decomposition temperature of resin B was measured using a thermal analyzer STA7200 manufactured by Hitachi High-Tech Science. The measurement was performed under a nitrogen purge atmosphere of 200 mL / min. A 10 mg sample was placed in an aluminum pan, kept at 25°C for 10 minutes, and then heated to 600°C at a heating rate of 10°C / min. The temperature (Td5) at which the initial mass was reduced by 5% was taken as the thermal decomposition temperature.

[0115] In the composition of the present disclosure, MFR of fluororesin A / MFR of resin B may be 0.2 to 10, but is preferably 0.3 or more, more preferably 0.5 or more, and is preferably 5 or less, more preferably 3 or less, from the viewpoint of affinity between fluororesin A and resin B.

[0116] When calculating MFR of fluororesin A / MFR of resin B, the MFR of each resin is measured at the same temperature. The measurement temperature is a temperature close to the kneading temperature when fluororesin A and resin B are kneaded (molding temperature of resin B), specifically 325°C.

[0117] The MFR of each resin is a value obtained as follows: the mass (g / 10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm every 10 minutes at 325°C x 2.16 kg load using a melt flow indexer (manufactured by Yasuda Seiki Co., Ltd.) in accordance with ASTM D1238, and the value obtained using the mass.

[0118] The MFR of the fluororesin A 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, and even more preferably 100 g / 10 min or more, and is 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.

[0119] Regarding the MFR of resin B at 325°C, there is no particular limitation as long as it is within the range that satisfies the above relationship, but it is preferably 30 g / 10 minutes or more, more preferably 50 g / 10 minutes or more, and further preferably 100 g / 10 minutes or more. In addition, it is preferably 1000 g / 10 minutes or less, more preferably 800 g / 10 minutes or less, and further preferably 500 g / 10 minutes or less.

[0120] The MFR of resin B at melting point + 8°C may be 30 g / 10 min or more, preferably 40 g / 10 min or more, more preferably 60 g / 10 min or more, and preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, further preferably 700 g / 10 min or less.

[0121] The MFR of the resin B at 8° C. was measured in the same manner as the MFR at 325° C. except that the measurement temperature was different.

[0122] In the composition of the present disclosure, the content of the fluororesin A is preferably 10% by volume or more, more preferably 20% by volume or more, and further preferably 25% by volume or more, and is preferably 45% by volume or less, more preferably 40% by volume or less, and further preferably 35% by volume or less.

[0123] In the composition of the present disclosure, the content of resin B is preferably 55% by volume or more, more preferably 60% by volume or more, and further preferably 65% ​​by volume or more, and is preferably 90% by volume or less, more preferably 80% by volume or less, and further preferably 75% by volume or less.

[0124] In the composition of the present disclosure, the total content of the fluororesin A and the 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.

[0125] In the composition of the present 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, further preferably 25 / 75 or more, and is preferably 45 / 55 or less, more preferably 40 / 60 or less, further preferably 35 / 65 or less.

[0126] The composition of the present disclosure may contain a fluororesin C which does not correspond to the fluororesin A. The fluororesin C is not particularly limited as long as it does not satisfy the relationship of MFR of fluororesin C / MFR of resin B=0.2-10.

[0127] When calculating the MFR of fluororesin C / MFR of resin B, the MFR of each resin is measured by the same method as when calculating the MFR of fluororesin A / MFR of resin B.

[0128] It should be noted that the fluororesin A, resin B and fluororesin C may be used alone or in combination of two or more.

[0129] The compositions of the present disclosure may also include additives.

[0130] As the additive, epoxy compounds, amine compounds, oxazoline compounds, acid anhydrides, etc. can be used. Among them, oxazoline compounds are preferred.

[0131] As the oxazoline compound, there is no particular limitation as long as it has one or more oxazoline groups, preferably a compound having two or more oxazoline groups, and more preferably a compound having 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.

[0132] The oxazoline compound may be an oligomer or a polymer having an oxazoline group. Specific examples of polymers having an oxazoline group include poly-2-vinyl-2-oxazoline [Pvozo] and the like.

[0133] Fillers can also be used as additives. Specific examples of fillers include inorganic compounds such as silicon dioxide (more specifically, crystalline silicon dioxide, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate, potassium titanate, aluminum nitride, indium oxide, aluminum oxide, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO); minerals such as montmorillonite, talc, mica, boehmite, kaolin, montmorillonite, xonotlite, vermiculite, and sericite; carbon compounds such as carbon black, acetylene black, ketjen black, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes, and glass hollow spheres; and the like.

[0134] As additives, in addition to the additives described above, general additives for 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.

[0135] Furthermore, resins other than the fluororesin A and the resin B may be used as additives.

[0136] In the composition of the present disclosure, the content of the additive is preferably 0.1% by volume or more, more preferably 1% by volume or more, and further preferably 3% by volume or more, and is preferably 15% by volume or less, more preferably 12% by volume or less, and further preferably 10% by volume or less.

[0137] <Molded article of the present disclosure>

[0138] The shaped body of the present disclosure includes the composition of the present disclosure.

[0139] The molded article of the present disclosure is obtained by molding the composition of the present disclosure. The molding method is not particularly limited, and conventional methods such as injection molding, blow molding, inflation molding, vacuum / air pressure molding, etc. can be used.

[0140] The shaped body of the present disclosure is preferably used as a dielectric material, in particular, a low-dielectric substrate material (eg, an insulating material).

[0141] It should be noted that in this specification, "low dielectric substrate material" refers to a material whose relative dielectric constant at 25°C and 10 GHz is less than 5.0 and whose dielectric loss tangent at 25°C and 10 GHz is less than 0.003, more preferably a material whose relative dielectric constant at 25°C and 10 GHz is less than 4.0 and whose dielectric loss tangent at 25°C and 10 GHz is less than 0.002, and further preferably a material whose relative dielectric constant at 25°C and 10 GHz is less than 3.5 and whose dielectric loss tangent at 25°C and 10 GHz is less than 0.0012.

[0142] When the molded body of the present invention is made into a dielectric material, there is no particular limitation on its use. For example, it can be used for electrical / electronic components such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed circuit boards, computer-related parts, etc.; semiconductor manufacturing process-related parts such as IC trays and wafer carriers, VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, lighting fixtures and other household electrical product parts, lamp reflectors, lamp holders and other lighting fixture parts, CDs, speakers and other audio product parts, optical cable ferrules, telephone parts, fax machine parts, modems and other communication equipment parts, separation claws, heater brackets and other copier-related parts, impellers, fans, gears, gears , bearings, motor parts and casings and other mechanical parts, automobile mechanism parts, engine parts, engine compartment parts, electrical parts, interior parts and other automobile parts, microwave cooking pots, heat-resistant tableware and other cooking utensils, floor materials, wall materials and other insulation, sound insulation materials, beams, columns and other supporting materials, roof materials and other building materials or civil engineering materials, aircraft, spacecraft, space equipment parts, nuclear reactors and other radiation facility parts, marine facility parts, cleaning fixtures, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary equipment, etc.

[0143] <Laminate of the Present Disclosure>

[0144] The laminated body of the present disclosure includes a metal foil and the formed body of the present disclosure.

[0145] As the metal of the metal foil, aluminum, iron, silver, gold, ruthenium, etc. can be cited. In addition, their alloys can also be used. Among them, copper is preferred. As copper, rolled copper, electrolytic copper, etc. can be used.

[0146] The thickness of the laminate of the present disclosure is preferably 10 μm to 1000 μm. In addition, in the laminate of the present disclosure, the thickness of the molded product of the present disclosure is preferably 1 μm to 100 μm.

[0147] The layered product and molded product of the present disclosure are preferably in the form of a sheet having a substantially constant thickness. However, when there are portions with different thicknesses, the thicknesses of 10 portions divided at equal intervals in the longitudinal direction are measured and averaged.

[0148] The laminate of the present disclosure may further include other layers laminated in addition to the above-mentioned metal foil and the molded product of the present disclosure.

[0149] The laminated body disclosed in the present invention is preferably used as a circuit substrate, particularly a printed circuit substrate, a laminated circuit substrate (multilayer substrate), or a high-frequency circuit substrate.

[0150] The high-frequency circuit substrate is a circuit substrate that can also work in a high-frequency band. The high-frequency band can be a band above 1 GHz, preferably a band above 3 GHz, and more preferably a band above 5 GHz. The upper limit is not particularly limited, and can be a band below 100 GHz.

[0151] <Manufacturing method disclosed herein>

[0152] In the production method of the present invention, a composition containing fluororesin A and resin B is obtained through an MFR adjustment step of adjusting (MFR of fluororesin A) / (MFR of resin B (excluding fluororesin A) having a melt flow rate of 30 g / 10 minutes or more at melting point + 8°C) to 0.2 to 10.

[0153] As the fluororesin A and the resin B, the same ones as those in the above-mentioned composition of the present disclosure can be used.

[0154] In the MFR adjustment step, the MFR of any resin may be adjusted, but it is preferred to adjust at least the MFR of the fluororesin so as to obtain the fluororesin A satisfying MFR of fluororesin A / MFR of resin B=0.2-10.

[0155] In addition, the method for adjusting the MFR is not particularly limited, but the molecular weight of the resin is preferably adjusted. As the method for adjusting the molecular weight of the resin, there can be cited a method of adopting a polymerization method to reduce the molecular weight of the resin, a method of reducing the molecular weight of the resin by shearing during kneading, a method of reducing the molecular weight of the resin by irradiation of ionizing radiation, etc. That is, in the MFR adjustment step, it is preferred to obtain the fluororesin A by polymerization, kneading or irradiation of ionizing radiation.

[0156] The polymerization method for reducing the molecular weight of the resin is not particularly limited, and the materials and reaction conditions may be appropriately set according to the desired molecular weight.

[0157] When the molecular weight of the resin is reduced by shearing during kneading, the shear rate is preferably 100 seconds. -1 ( / second) or more. The upper limit is not particularly limited, for example, 5000 seconds -1 ( / second) or less.

[0158] In addition, the shear rate (γ) is a value calculated|required using the following formula, for example.

[0159] γ=πDr / C

[0160] D: screw outer diameter (mm)

[0161] r: screw speed (rpm)

[0162] C: Outer diameter clearance (mm)

[0163] Ionizing radiation is radiation that ionizes matter and is classified into particle beams and electromagnetic waves. Particle beams are further classified into charged particle beams such as α rays and β rays, and uncharged particle beams such as neutron rays. Electromagnetic waves include X-rays, γ rays, etc.

[0164] In addition, ionizing rays can also be classified into direct ionizing rays and indirect ionizing rays. In this case, charged particle beams correspond to direct ionizing rays, and uncharged particle beams and electromagnetic waves correspond to indirect ionizing rays.

[0165] From the viewpoint of energy penetration throughout the entire resin, the ionizing radiation is preferably an indirect ionizing radiation, more preferably an electromagnetic wave, and still more preferably a gamma ray.

[0166] The fluororesin to be irradiated with ionizing radiation is preferably a melt-processable fluororesin. In the present specification, melt-processable means that the polymer can be melt-processed using conventional processing equipment such as an extruder and an injection molding machine.

[0167] Examples of the melt-processable fluororesin include the above-mentioned PFA, FEP, ETFE, EFEP, PCTFE, PVdF, etc. From the viewpoint of affinity with the resin B, at least one selected from the group consisting of PFA and FEP is preferred, and FEP is more preferred.

[0168] The above embodiments are described, but it should be understood that various changes can be made in mode and detail without departing from the spirit and scope of the claims.

[0169] Example

[0170] Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0171] The materials used in the examples are as follows.

[0172] (Fluororesin) (It should be noted that in the following examples, FEP (2) and (3) correspond to fluororesin A)

[0173] FEP (1) (TFE unit / HFP unit (molar ratio) = 88.0 / 12.0, MFR (325°C): 5.6 g / 10 min, thermal decomposition temperature: 427°C)

[0174] FEP (2) (synthesized by the following method, TFE unit / HFP unit / PPVE unit (molar ratio) = 90.9:8.80:0.35, MFR (325°C): 228.0 g / 10, thermal decomposition temperature: 470°C)

[0175] FEP (3) (synthesized by the following method, TFE unit / HFP unit (molar ratio) = 88.0 / 12.0, MFR (325°C): 270.2 g / 10, thermal decomposition temperature: 463°C)

[0176] (Resin B)

[0177] LCP (1) (Type II liquid crystal polymer, melting point: 313°C, MFR (325°C): 206.5 g / 10 min, MFR (321°C (melting point + 8°C)): 62.4 g / 10 min, thermal decomposition temperature: 501°C)

[0178] LCP (2) (Type II liquid crystal polymer, melting point: 322°C, MFR (325°C): 206.7 g / 10 min, MFR (330°C (melting point + 8°C)): 648.4 g / 10 min, thermal decomposition temperature: 501°C)

[0179] Synthesis method of FEP(2)

[0180] 1100g of deoxygenated ion exchange water was added to a glass-lined autoclave with an internal volume of 4L, the interior of the autoclave was evacuated, and 1100g of hexafluoropropylene (HFP) was added, and the temperature in the autoclave was maintained at 28°C. Next, 8.0g of perfluoropropyl vinyl ether (PPVE) and 5.0g of methanol were added to the autoclave, and tetrafluoroethylene (TFE) was pressed into the autoclave to 0.89MPaG under stirring. Next, 8.0g of diisopropyl peroxydicarbonate was added to start polymerization. Since the pressure decreases as the polymerization proceeds, the polymerization was carried out for 10.6 hours while additional tetrafluoroethylene was pressed into the autoclave to maintain the polymerization pressure at 0.89MPaG. After the polymerization was completed, the residual monomers and solvents were recovered, and the product was washed and dried to obtain 74g of polymerization powder.

[0181] Synthesis method of FEP (3)

[0182] An aluminum card bag containing 1000 g of FEP pellets was placed on a conveyor belt and irradiated with 500 kGy of gamma rays while moving around a radiation source, and then degassed at 200°C for 4 hours to obtain a sample.

[0183] Examples and Comparative Examples

[0184] Using a circulating twin-screw extruder (Xplore MC15HT, manufactured by Xplore Instruments), 13.72 g of resin B and 9.03 g of fluororesin were mixed under the conditions in Table 1. The materials were pre-dry mixed and fed from the feed hopper and mixed for 5 minutes at 500 rpm. The mixing temperature was the conditions in Table 1. After mixing, the sample was collected as a strand.

[0185] The cross section of the obtained strands was observed with a laser microscope to evaluate the morphology after kneading (dispersion state of the resin). It was confirmed that a sea-island structure was formed in which the resin B was the sea and the fluororesin was the island. However, compared with the comparative example, the dispersed particle size of the island (fluororesin) in the example was smaller and the dispersion state was good. In addition, the appearance of the strands was also good.

[0186] In addition, the evaluation criteria of the strand appearance are as follows.

[0187] A: No roughness or agglomeration is observed on the surface of the strands.

[0188] B: The surface of the wire can be seen to be rough and coagulated.

[0189] [Table 1]

[0190]

Claims

1. A composition comprising a fluororesin A and a resin B having a melt flow rate of 30 g / 10 min or more at a melting point of +8°C, wherein the resin B does not include the fluororesin A. The fluororesin A is a resin satisfying MFR of the fluororesin A / MFR of the resin B=0.2-10.

2. The composition according to claim 1, wherein The MFR of the fluororesin A is 30 g / 10 minutes 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) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.

4. The composition according to any one of claims 1 to 3, wherein The resin B is at least one selected from the group consisting of liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryletherketone, polysulfone and polyethersulfone.

5. The composition according to any one of claims 1 to 4, wherein The content of the fluororesin A is 10 volume % or more.

6. The composition according to any one of claims 1 to 5, wherein The dispersed particle size of the fluororesin A is 5.0 μm or less.

7. The composition according to any one of claims 1 to 6, comprising an additive. 8 . A molded product comprising the composition according to claim 1 .

9. The molded body according to claim 8, which is used for a low dielectric substrate material. 10 . A laminate comprising a metal foil and the formed body according to claim 8 or 9 .

11. The laminate according to claim 10, wherein The metal foil is copper.

12. A method for producing a composition, wherein a composition comprising the fluororesin A and the resin B is obtained through an MFR adjustment step of adjusting (MFR of fluororesin A) / (MFR of resin B) to 0.2 to 10, wherein the resin B does not include the fluororesin A and has a melt flow rate of 30 g / 10 min or more at a melting point of +8°C.

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

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