Composition, molded article, laminated body, and method for producing 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] The present disclosure relates to a composition, a molded body, a laminate, and a method for producing the composition. [Background technology]

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

[0003] [Patent Document 1] JP 2001-187833 A [Patent Document 2] JP 2018-177931 A [Patent Document 3] JP 2019-065061 A Summary of the Invention [Problem to be solved by the invention]

[0004] The inventors of the present invention have found that increasing the proportion of fluororesin, as is done in the examples of Patent Documents 2 and 3, reduces the affinity between the liquid crystal polymer and the fluororesin, making the fluororesin more likely to aggregate (poorly dispersed). Since aggregation of the fluororesin causes poor appearance of the strands, it is preferable to prevent it from occurring as much as possible.

[0005] An object of the present disclosure is to provide a composition, a molded body, a laminate, and a method for producing the composition, which are capable of suppressing aggregation of the fluororesin, which causes poor appearance of strands, even when the proportion of the fluororesin is increased. [Means for solving the problem]

[0006] The present disclosure (1) comprises 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 that is a resin that satisfies the relationship of MFR of the fluororesin A / MFR of the resin B=0.2 to 10 (hereinafter, also referred to as "the composition of the present disclosure").

[0007] The present disclosure (2) is the composition according to the present disclosure (1), in which the fluororesin A has an MFR of 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 tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.

[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 polyethersulfone.

[0010] The present disclosure (5) is the composition according to any one of the present disclosures (1) to (4), in which 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 size of the fluororesin A is 5.0 μm or less.

[0012] The present disclosure (7) is a 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 containing the composition according to any one of the present disclosures (1) to (7) (hereinafter also referred to as "the molded article of the present disclosure").

[0014] The present disclosure (9) is the molded article according to the present disclosure (8) used for a low dielectric substrate material.

[0015] The present disclosure (10) is a laminate (hereinafter also referred to as "the laminate of the present disclosure") including a metal foil and the molded body according to the present disclosure (8) or (9).

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

[0017] The present disclosure (12) is a method for producing a composition containing a fluororesin A and a resin B, comprising: a 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 min or more at melting point + 8° C.) to 0.2 to 10 (hereinafter, also referred to as the “production method of the present disclosure”).

[0018] The present disclosure (13) relates to the method for producing the composition according to the present disclosure (12), wherein in the MFR adjusting step, the fluororesin A is obtained by polymerization, kneading, or irradiation with ionizing radiation. Effect of the Invention

[0019] According to the present disclosure, it is possible to provide a composition, a molded body, a laminate, and a method for producing the composition, which are capable of suppressing aggregation of the fluororesin, which causes poor appearance of the strands, even when the proportion of the fluororesin is increased. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] As used herein, "organic group" means a group containing one or more carbon atoms or a group formed by removing a hydrogen atom from an organic compound. Examples of the "organic group" are: an alkyl group which may have one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents, Cyano group, Formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2- and RaNRbSO2- (In these formulas, Ra is independently an alkyl group which may have one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents, Rb is independently H or an alkyl group which may have one or more substituents. Includes: The organic group is preferably an alkyl group which may have one or more substituents.

[0021] The present disclosure will now be described in detail.

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

[0023] According to the composition of the present disclosure, by adjusting the MFR of fluororesin A / MFR of resin B within the above range, it is possible to improve the affinity between fluororesin A and resin B. As a result, even when the proportion of fluororesin is increased, aggregation of fluororesin, which causes poor appearance of strands, can be suppressed.

[0024] Examples of the 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, and TFE / perfluoroalkyl allyl ether copolymer. Perfluoroalkyl allyl ether is CF2=CFCF2-O-Rf 4 (Rf 4 is a monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms.

[0025] As the fluororesin A, from the viewpoint of affinity with the 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, and FEP is more preferred.

[0026] The perfluorovinyl ether is not particularly limited, and may be, for example, a perfluorovinyl ether represented by the following general formula (1): CF2=CF-ORf (1) (wherein Rf represents a perfluoro organic group). In this specification, the "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoro organic group may have an ether oxygen.

[0027] An example of the perfluorovinyl ether is perfluoro(alkyl vinyl ether) [PAVE], which is represented by the general formula (1) in which Rf 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 the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Preferred is purpuro(propyl vinyl ether) [PPVE], in which the perfluoroalkyl group is a perfluoropropyl group.

[0029] Further, the perfluorovinyl ether includes those represented by the general formula (1), in which Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and those represented by the following formula:

[0030] [ka]

[0031] (wherein m represents 0 or an integer of 1 to 4), Rf is a group represented by the following formula:

[0032] [ka]

[0033] (wherein n represents an integer of 1 to 4).

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

[0035] The PFA is not particularly limited, but is preferably a copolymer having a molar ratio of TFE units and PAVE units (TFE units / PAVE units) 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 an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The PFA preferably contains 0.1 to 10 mol % of monomer units derived from a monomer copolymerizable with TFE and PAVE (a copolymer containing 90 to 99.9 mol % of TFE units and PAVE units in total), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0036] Monomers copolymerizable with TFE and PAVE include HFP, a copolymer of the formula (I): CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (In the formula, Z 1 , Z 2 and Z 3 are the same or different and each represents a hydrogen atom or a fluorine atom; Z 4represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10. 1 (In the formula, Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms. 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 and each represents 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. Examples of the allyl ether monomer include an allyl ether monomer represented by CH2=CFCF2-O-Rf 4 , CF2=CFCF2-O-Rf 4 (Perfluoroalkylaryl ether), CF2=CFCH2-O-Rf 4 , CH2=CHCF2-O-Rf 4 (In the formula, Rf 4 is the same as the above formula (X). Further examples of 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 anhydride.

[0037] The melting point of PFA is preferably from 180 to less than 324°C, more preferably from 230 to 320°C, and even more preferably from 280 to 320°C.

[0038] The FEP is not particularly limited, but is preferably a copolymer having a molar ratio of TFE units and HFP units (TFE units / HFP units) 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 an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The FEP preferably contains 0.1 to 10 mol % of monomer units derived from a monomer copolymerizable with TFE and HFP (a copolymer containing 90 to 99.9 mol % of TFE units and HFP units in total), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0039] Examples of monomers copolymerizable with TFE and HFP include PAVE, a monomer represented by formula (X), an alkyl perfluorovinyl ether derivative represented by formula (II), etc. Examples of monomers copolymerizable with TFE and HFP also 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 anhydride.

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

[0041] The ETFE is preferably a copolymer having a molar ratio of TFE units to ethylene units (TFE units / ethylene units) of 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 an even more preferred molar ratio is 38 / 62 or more and 80 / 20 or less. The ETFE may be a copolymer consisting of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene. The ETFE preferably contains 0.1 to 10 mol % of monomer units derived from TFE and a monomer copolymerizable with ethylene (a copolymer containing 90 to 99.9 mol % of TFE units and ethylene units in total), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0042] The monomer copolymerizable with TFE and ethylene is represented by 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.) and a monomer represented by formula (X), among which CF2=CFRf 2 , CF2=CFORf 2 and CH2=CX 1 Rf 2 and a monomer represented by the formula (X) is preferred, and HFP, CF2=CF-ORf 3 (In the formula, Rf 3 represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Perfluoro(alkyl vinyl ether) represented by CF2=CF-CF2-O-Rf 4 (In the formula, Rf 4 Rf represents a perfluoroalkyl group having 1 to 5 carbon atoms. 2 is a fluoroalkyl group having 1 to 8 carbon atoms, CH2=CX 1 Rf 2 More preferred is a fluorine-containing vinyl monomer represented by the following formula: Furthermore, examples of the monomer copolymerizable with TFE and ethylene 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 anhydride.

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

[0044] The content of each monomer unit in the above-mentioned polymer 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 the fluororesin A is preferably 330°C or higher, more preferably 350°C or higher, and even more preferably 370°C or higher, and is 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 thermal analyzer STA7200 manufactured by Hitachi High-Tech Science Corporation. The measurement was performed under a nitrogen purge atmosphere at 200 mL / min. 10 mg of 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 temperature at which the mass decreased by 5% from the initial mass (Td5) was taken as the thermal decomposition temperature. Furthermore, in the case where the fluororesin A has been irradiated with ionizing radiation to reduce its molecular weight, the thermal decomposition temperature is measured after the irradiation with ionizing radiation and then a degassing operation.

[0047] Fluorine resin A has a main chain carbon number of 10 6 Each of the monomers may have 100 to 2000 unstable terminal groups. The unstable terminal groups are -COF and -COOH, and the above number is the total number of these.

[0048] The number of unstable terminal groups can be measured by infrared spectroscopy. Specifically, fluororesin A is first melt extruded to produce a film having a thickness of 0.25 to 0.3 mm. This film is analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum of fluororesin A, and a difference spectrum is obtained from a base spectrum in which the fluororesin is completely fluorinated and has no unstable terminal groups. From the absorption peaks of specific unstable terminal groups that appear in this difference spectrum, the number of carbon atoms in fluororesin A can be calculated according to the following formula (A): 6 The number of unstable terminal groups per unit, N, is calculated. N=I×K / t (A) I: Absorbance K: Correction coefficient t: film thickness (mm)

[0049] The composition of the present disclosure preferably forms a sea-island structure in which resin B is the sea and fluororesin A is the islands.

[0050] 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 even more preferably 2.0 μm or less. There is no particular lower limit, but a size of 0.1 μm or more is preferred.

[0051] The dispersed particle size of the fluororesin A is determined according to the following procedure. First, a test piece is obtained by cutting the composition perpendicular to the longitudinal direction, and the cross section is observed with a confocal laser microscope. The obtained microscopic image is analyzed using image analysis software (Image J) to obtain the circle equivalent diameter of the dispersed phase. Then, the circle equivalent diameters of 20 dispersed phase particles 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 +8° C., but examples of resins that can be used include liquid crystal polymers, polyetherimides, polyphenylene sulfides, polyaryl ether ketones, polysulfones, polyether sulfones, etc. Among these, at least one selected from the group consisting of liquid crystal polymers, polyetherimides, polyphenylene sulfides, polyaryl ether ketones, polysulfones, and polyether sulfones is preferred, and liquid crystal polymers are particularly preferred.

[0053] The liquid crystal polymer is not particularly limited, but may be a polymer having a liquid crystallization temperature (i.e., melting point) of 180° C. to 380° C., and is preferably a thermotropic liquid crystal polymer that becomes a liquid crystal state such as a nematic state when heated. For example, Type I liquid crystal polymer (biphenol / benzoic acid / paraoxybenzoic acid (POB) copolymer, etc.) Type II liquid crystal polymers (Hydroxynaphthoic acid (HNA) / POB copolymers, etc.) Type III liquid crystal polymer (POB / ethylene terephthalate copolymer, etc.) Among these, from the viewpoints of kneading temperature and liquid crystal transition temperature, at least one selected from the group consisting of I-type liquid crystal polymers and II-type liquid crystal polymers is preferred, and II-type 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 is preferably 380° C. or lower, more preferably 350° C. or lower.

[0055] As the polyetherimide, for example, one having an imide bond and an ether bond in the molecule can be used.

[0056] 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.

[0057] As the polyphenylene sulfide, for example, a resin having a structural unit represented by the following formula can be used: The proportion of this structural unit is preferably 70 mol % or more. -(Ph-S)- In the formula, Ph 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, amido-substituted phenylene, p,p'-diphenylene sulfone, p,p'-biphenylene, p,p'-biphenylene ether, etc. 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 is preferably 380° C. or lower, more preferably 350° C. or lower.

[0059] Examples of polyaryletherketones include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), etc. 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 is preferably 400° C. or lower, more preferably 380° C. or lower.

[0061] There are no particular limitations on the polysulfone, and any commonly used polysulfone can be used.

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

[0063] The polyethersulfone is not particularly limited, and a general polyethersulfone can be used.

[0064] The glass transition temperature of the polyethersulfone is preferably 180° C. or higher, more preferably 200° C. or higher, and even more preferably 220° C. or higher, and is 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 ​​on the heat of fusion curves 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 by obtaining a DSC curve using a differential scanning calorimeter (Mettler Toledo, DSC822e) by heating 10 mg of a sample at 10°C / min. The temperature is the midpoint between the two intersections of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent to 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 is preferably 600° C. or lower, more preferably 550° C. or lower.

[0067] The thermal decomposition temperature of resin B was measured using a thermal analyzer STA7200 manufactured by Hitachi High-Tech Science Corporation. The measurement was performed under a nitrogen purge atmosphere at 200 mL / min. 10 mg of 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 temperature at which the mass decreased by 5% from the initial mass (Td5) was taken as the thermal decomposition temperature.

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

[0069] When calculating the MFR of fluororesin A / MFR of 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 mixing fluororesin A and resin B, specifically, 325°C. The MFR of each resin is a value obtained in accordance with ASTM D1238 using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) as the mass of polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2 mm and a length of 8 mm 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 it is within a range that 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 is preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, 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 is within a range that 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 is preferably 1000 g / 10 min or less, more preferably 800 g / 10 min or less, even more preferably 500 g / 10 min or less.

[0071] The MFR of Resin B at the melting point +8°C may be 30 g / 10 min or more, but is preferably 40 g / 10 min or more, more preferably 60 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 700 g / 10 min or less.

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

[0073] In the composition of the present disclosure, the content of fluororesin A is preferably 10 vol% or more, more preferably 20 vol% or more, even more preferably 25 vol% or more, and preferably 45 vol% or less, more preferably 40 vol% or less, even more preferably 35 vol% or less.

[0074] In the composition of the present disclosure, the content of resin B is preferably 55 vol% or more, more preferably 60 vol% or more, even more preferably 65 vol% or more, and is preferably 90 vol% or less, more preferably 80 vol% or less, even more preferably 75 vol% or less.

[0075] In the composition of the present 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. There is no particular upper limit, and it may be 100% by volume.

[0076] 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, even more preferably 25 / 75 or more, and is preferably 45 / 55 or less, more preferably 40 / 60 or less, even more preferably 35 / 65 or less.

[0077] The composition of the present disclosure may contain a fluororesin C that does not fall under the category of 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. When calculating the MFR of fluororesin C / MFR of resin B, the MFR of each resin is measured in the same manner as when calculating the MFR of fluororesin A / MFR of resin B.

[0078] The above-mentioned fluororesin A, resin B, and fluororesin C may be used alone or in combination of two or more kinds.

[0079] The compositions of the present disclosure may further comprise additives.

[0080] As the additive, an epoxy compound, an amine compound, an oxazoline compound, an acid anhydride, etc. can be used. Among them, an oxazoline compound is preferable.

[0081] The oxazoline compound is not particularly limited as long as it has one or more oxazoline groups, but it is preferably one having two or more oxazoline groups, and more preferably one 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. The oxazoline compound may be an oligomer or polymer having an oxazoline group. A specific example of a polymer having an oxazoline group is 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 oxide, 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, 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; and various glasses such as glass beads, glass flakes, and glass balloons.

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

[0084] In the composition of the present disclosure, the content of the additive is preferably 0.1 vol.% or more, more preferably 1 vol.% or more, even more preferably 3 vol.% or more, and preferably 15 vol.% or less, more preferably 12 vol.% or less, even more preferably 10 vol.% or less.

[0085] <Molded body of the present disclosure> The molded article of the present disclosure comprises the composition of the present disclosure.

[0086] The molded article of the present disclosure can be obtained by molding the composition of the present disclosure. The molding method is not particularly limited, and a typical method such as injection molding, blow molding, inflation molding, vacuum / pressure molding, etc. can be used.

[0087] The molded article of the present disclosure is suitably used as a dielectric material, in particular, a low dielectric substrate material (for example, an insulating material). In this specification, a "low dielectric substrate material" refers to a material having a dielectric constant of 5.0 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.003 or less at 25°C and 10 GHz, more preferably a material having a dielectric constant of 4.0 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.002 or less at 25°C and 10 GHz, and even more preferably a material having a dielectric constant of 3.5 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.0012 or less at 25°C and 10 GHz.

[0088] When the molded article of the present disclosure is used as a dielectric material, its application is not particularly limited. For example, it may be used in electrical and electronic parts such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, and computer-related parts; semiconductor manufacturing process-related parts such as IC trays and wafer carriers; home electrical product parts such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors and lamp holders; audio product parts such as compact discs and speakers; ferrules for optical cables, telephone parts, facsimile parts, and communication device parts such as modems; copier-related parts such as separation claws and heater holders; impellers. The material can be used for a wide range of applications, including mechanical parts such as fans, gears, bearings, motor parts and cases, automotive mechanism parts, engine parts, engine room parts, electrical parts, interior parts and other automotive parts, cooking utensils such as microwave cooking pots and heat-resistant tableware, heat insulation and soundproofing materials such as flooring and wall materials, support materials such as beams and pillars, building materials such as roofing materials or civil engineering and construction materials, aircraft, spacecraft, space equipment parts, radiation facility parts such as nuclear reactors, marine facility parts, cleaning tools, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and materials, sensor parts, sanitary equipment, etc.

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

[0090] Examples of the metal for the metal foil include aluminum, iron, silver, gold, and ruthenium. In addition, alloys of these metals can also be used. Among these, copper is preferred. Examples of copper that can be used include rolled copper and electrolytic copper.

[0091] The thickness of the laminate of the present disclosure is preferably 10 μm to 1000 μm. In the laminate of the present disclosure, the molded article of the present disclosure preferably has a thickness of 1 μm to 100 μm. The laminates and molded articles of the present disclosure are preferably in the form of sheets having a substantially uniform thickness. However, if there are portions of differing thickness, the thicknesses of 10 equally spaced points along the longitudinal direction are measured and the average is calculated.

[0092] The laminate of the present disclosure may have other layers laminated thereon in addition to the above-mentioned metal foil and the molded article of the present disclosure.

[0093] The laminate of the present disclosure is suitably used as a circuit board, in particular a printed circuit board, a laminated circuit board (multilayer board), or a high-frequency circuit board.

[0094] The high-frequency circuit board is a circuit board that can operate in a high-frequency band. The high-frequency band may be a band of 1 GHz or more, preferably a band of 3 GHz or more, and more preferably a band of 5 GHz or more. There is no particular upper limit, but it may be a band of 100 GHz or less.

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

[0096] The fluororesin A and resin B can be the same as those in the composition of the present disclosure described above.

[0097] In the MFR adjusting step, the MFR of either resin may be adjusted, but it is preferable to adjust the MFR of at least the fluororesin to obtain a fluororesin A that satisfies MFR of fluororesin A / MFR of resin B=0.2-10. The method for adjusting the MFR is not particularly limited, but it is preferable to adjust the molecular weight of the resin. Examples of the method for adjusting the molecular weight of the resin include a method of adopting a polymerization method that reduces the molecular weight of the resin, a method of reducing the molecular weight of the resin by shearing during kneading, and a method of reducing the molecular weight of the resin by irradiating with ionizing radiation. That is, in the MFR adjustment step, it is preferable to obtain the fluororesin A by polymerization, kneading, or irradiation with ionizing radiation.

[0098] There are no particular limitations on the polymerization method for reducing the molecular weight of the resin, and the materials and reaction conditions may be appropriately set in accordance with the expected molecular weight.

[0099] When reducing the molecular weight of the resin by shear during kneading, the shear rate is 100 s -1 ( / sec) or more. The upper limit is not particularly limited, but for example, 5000 seconds -1 ( / sec) or less. The shear rate (γ) is a value 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 (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 alpha rays and beta rays, and uncharged particle beams such as neutron beams. Electromagnetic waves include X-rays and gamma rays. Ionizing radiation can also be classified into direct ionizing radiation and indirect ionizing radiation, where charged particle beams correspond to direct ionizing radiation, and non-charged particle beams and electromagnetic waves correspond to indirect ionizing radiation. In terms of the penetration of energy into the entire resin, the ionizing radiation is preferably indirect ionizing radiation, more preferably electromagnetic waves, and even more preferably gamma rays.

[0101] The fluororesin to be irradiated with ionizing radiation is preferably a melt-processable fluororesin, where 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 the melt-processable fluororesin include the above-mentioned 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, and FEP is more preferred.

[0103] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0104] The present disclosure will now be described in more detail 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) (In the following examples, FEP (2) and (3) correspond to fluororesin A.) 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) 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) 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) (Resin B) LCP(1) (II type liquid crystal polymer, melting point: 313℃, MFR(325℃): 206.5g / 10min, MFR(321℃(melting point+8℃)): 62.4g / 10min, thermal decomposition temperature: 501℃) LCP(2) (II type 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] Synthesis method of FEP(2) In a glass-lined autoclave with an internal volume of 4 L, 1100 g of deoxygenated ion-exchanged water was placed, the inside of the autoclave was evacuated, 1100 g of hexafluoropropylene (HFP) was placed, and the temperature inside the tank was kept at 28 ° C. Next, 8.0 g of perfluoropropyl vinyl ether (PPVE) and 5.0 g of methanol were placed in the autoclave, and tetrafluoroethylene (TFE) was pressed up to 0.89 MPaG under stirring. Next, 8.0 g of di-iso-propyl peroxydicarbonate was placed to start polymerization. Since the pressure decreased with the progress of polymerization, tetrafluoroethylene was additionally pressed in to maintain the polymerization pressure at 0.89 MPaG, and polymerization was carried out for 10.6 hours. After the polymerization was completed, the remaining monomer and solvent were collected, and the product was washed and dried to obtain 74 g of polymerized powder.

[0107] Synthesis of FEP(3) An aluminum zipper bag containing 1000g of FEP pellets was placed on a belt conveyor and irradiated with 500kGy of gamma rays while moving around the radiation source. After that, the bag was degassed at 200℃ for 4 hours to obtain a sample.

[0108] Examples and Comparative Examples Using a circulating twin-screw extruder (Xplore MC15HT: manufactured by Xplore Instruments), we investigated the kneading of 13.72 g of resin B and 9.03 g of fluororesin under the conditions in Table 1. The materials were dry blended in advance and then added from a hopper and kneaded at 5 min and 500 rpm. The kneading temperature was as shown in Table 1. After kneading, samples were collected as strands. The cross section of the obtained strand was observed with a laser microscope to evaluate the morphology (resin dispersion state) after kneading. In both cases, a sea-island structure was formed in which resin B was the sea and the fluororesin was the island, but it was confirmed that the dispersed particle size of the islands (fluororesin) was smaller in the example than in the comparative example, and the dispersion state was better. In addition, the appearance of the strand was also good. The evaluation criteria for the appearance of the strands were as follows: A: No roughness or clumping is observed on the strand surface. B: Roughness or clumping is 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. A composition in which the volume ratio of fluororesin A to resin B (fluororesin A / resin B) is 45 / 55 or less.

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 resin B is at least one selected from the group consisting of liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyarylether ketone, polysulfone, and polyethersulfone.

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

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

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

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

9. A molded article according to claim 8, used in a low dielectric substrate material.

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

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

12. 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, A method for producing a composition in which the volume ratio of fluororesin A to resin B (fluororesin A / resin B) is 45 / 55 or less.

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