阅读说明：本技术 树脂组合物和成型品 (Resin composition and molded article ) 是由 仲西幸二 关丰光 河野英树 于 2020-03-19 设计创作，主要内容包括：本发明提供一种树脂组合物,其不会引起表面剥离,能够制造出拉伸断裂伸长率优异、进而低介电常数性也优异的成型品。一种树脂组合物,其是包含芳香族聚醚酮树脂(I)和含氟共聚物(II)的树脂组合物,其特征在于,含氟共聚物(II)的平均分散粒径r1与含氟共聚物(II)的平均分散粒径r2之比r2/r1为1.60以下,该平均分散粒径r2是依据ASTM D1238在380℃、5000g负荷下并进行5分钟预热而对熔体流动速率进行测定后的含氟共聚物(II)的平均分散粒径。(The invention provides a resin composition which does not cause surface peeling and can produce a molded product with excellent tensile elongation at break and low dielectric constant. A resin composition comprising an aromatic polyether ketone resin (I) and a fluorocopolymer (II), wherein the ratio r2/r1 of the average dispersed particle diameter r1 of the fluorocopolymer (II) to the average dispersed particle diameter r2 of the fluorocopolymer (II) is 1.60 or less, and the average dispersed particle diameter r2 is the average dispersed particle diameter of the fluorocopolymer (II) measured by preheating at 380 ℃ under a load of 5000g for 5 minutes in accordance with ASTM D1238 and measuring the melt flow rate.)

1. A resin composition comprising an aromatic polyether ketone resin (I) and a fluorocopolymer (II), wherein the ratio r2/r1 of the average dispersed particle diameter r1 of the fluorocopolymer (II) to the average dispersed particle diameter r2 of the fluorocopolymer (II) is 1.60 or less, and the average dispersed particle diameter r2 is the average dispersed particle diameter of the fluorocopolymer (II) measured by preheating at 380 ℃ under a load of 5000g for 5 minutes in accordance with ASTM D1238 and measuring the melt flow rate.

2. The resin composition according to claim 1, wherein the aromatic polyether ketone resin (I) has a melting point of 300 to 380 ℃.

3. The resin composition according to claim 1 or 2, wherein the glass transition temperature of the aromatic polyether ketone resin (I) is 130 to 220 ℃.

4. The resin composition according to any one of claims 1 to 3, wherein the melting point of the fluorocopolymer (II) is from 200 ℃ to 323 ℃.

5. The resin composition according to any one of claims 1 to 4, wherein the fluorine-containing copolymer (II) is a copolymer of tetrafluoroethylene and a perfluoroethylenically unsaturated compound represented by the following general formula (1),

CF₂＝CF-Rf¹ (1)

in the formula (1), Rf¹represents-CF₃or-ORf²，Rf²Represents a C1-5 perfluoroalkyl group.

6. The resin composition according to any one of claims 1 to 5, wherein the mass ratio of the aromatic polyether ketone resin (I) to the fluorine-containing copolymer (II) (I): (II) is 99:1 to 30: 70.

7. The resin composition according to any one of claims 1 to 6, further comprising a fibrous filler (III).

8. A pellet obtained by molding the resin composition according to any one of claims 1 to 7.

9. A molded article comprising the resin composition according to any one of claims 1 to 7 or the pellet according to claim 8.

Technical Field

The present invention relates to a resin composition and a molded article.

Background

Aromatic polyether ketone resins are known as super engineering plastics having excellent strength and heat resistance. Furthermore, fluororesins are excellent in properties such as sliding properties, heat resistance, chemical resistance, solvent resistance, weather resistance, flexibility, and electrical properties, and are used in various products.

For example, patent document 1 proposes a resin composition comprising an aromatic polyether ketone resin (I) and a fluororesin (II), wherein the fluororesin (II) is tetrafluoroethylene and a general formula (1)

CF₂＝CF-Rf¹ (1)

(wherein Rf¹represents-CF₃or-ORf²。Rf²A perfluoroalkyl group having 1 to 5 carbon atoms), wherein the mass ratio of the aromatic polyether ketone resin (I) to the fluororesin (II) (I): the ratio of (II) is 95:5 to 50:50, the fluororesin (II) is dispersed in the aromatic polyether ketone resin (I) in a granular form, and the average dispersed particle size of the fluororesin (II) is 3.0 [ mu ] m or less.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/005133

Disclosure of Invention

Problems to be solved by the invention

The invention provides a resin composition which does not cause surface peeling and can produce a molded product with excellent tensile elongation at break and low dielectric constant.

Means for solving the problems

The present invention relates to a resin composition comprising an aromatic polyether ketone resin (I) and a fluorocopolymer (II), wherein the ratio r2/r1 of the average dispersed particle diameter r1 of the fluorocopolymer (II) to the average dispersed particle diameter r2 of the fluorocopolymer (II) is 1.60 or less, and the average dispersed particle diameter r2 is the average dispersed particle diameter of the fluorocopolymer (II) measured by preheating at 380 ℃ under a load of 5000g for 5 minutes in accordance with ASTM D1238 and measuring the melt flow rate.

The melting point of the aromatic polyether ketone resin (I) is preferably 300 to 380 ℃.

The glass transition temperature of the aromatic polyether ketone resin (I) is preferably 130 to 220 ℃.

The melting point of the fluorine-containing copolymer (II) is preferably 200 to 323 ℃.

The fluorine-containing copolymer (II) is preferably tetrafluoroethylene and the following general formula (1):

CF₂＝CF-Rf¹ (1)

(wherein Rf¹represents-CF₃or-ORf²。Rf²A perfluoroalkyl group having 1 to 5 carbon atoms).

In the resin composition of the present invention, the mass ratio (I) of the aromatic polyether ketone resin (I) to the fluorine-containing copolymer (II) is: the ratio of (II) is preferably 99:1 to 30: 70.

The resin composition of the present invention preferably further contains a fibrous filler (III).

The present invention also relates to a pellet obtained by molding the resin composition.

The present invention also relates to a molded article comprising the resin composition or the pellet.

ADVANTAGEOUS EFFECTS OF INVENTION

The resin composition of the present invention, having the above-described structure, is less likely to cause surface peeling after molding, and can produce a molded article having excellent tensile elongation at break and further excellent low dielectric constant properties.

Detailed Description

The resin composition of the present invention comprises an aromatic polyether ketone resin (I) and a fluorine-containing copolymer (II). In the resin composition of the present invention, the fluorocopolymer (II) is preferably dispersed in the aromatic polyether ketone resin (I) in the form of particles. In such a case, usually, the aromatic polyether ketone resin (I) forms a continuous phase, and the fluorine-containing copolymer (II) forms a dispersed phase.

In the resin composition of the present invention, the ratio r2/r1 of the average dispersed particle diameter r1 of the fluorocopolymer (II) to the average dispersed particle diameter r2 of the fluorocopolymer (II) is 1.60 or less, and the average dispersed particle diameter r2 is the average dispersed particle diameter of the fluorocopolymer (II) measured by preheating at 380 ℃ under a load of 5000g for 5 minutes according to ASTM D1238 and measuring the Melt Flow Rate (MFR).

Since the fluorocopolymer is not easily mixed with other resins, a resin composition containing the fluorocopolymer causes surface peeling during molding and is not easily subjected to mechanical properties. The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a resin composition in which aggregation or coalescence of particles of a fluorocopolymer can be suppressed even when heated can be produced by focusing attention on the shear rate during kneading and carrying out shearing efficiently during kneading.

The resin composition of the present invention having the above-described structure can suppress surface peeling during molding. In addition, mechanical properties can be maintained even after molding, and a molded article having excellent tensile elongation at break can be produced. Furthermore, the molded article produced from the resin composition of the present invention is also excellent in impact resistance, toughness and flexibility. Further, the molded article obtained can have a low dielectric constant.

The above r1 represents the average dispersed particle diameter of the fluorocopolymer (II) in the resin composition of the present invention. The r2 represents the average dispersed particle diameter of the fluorocopolymer (II) in the resin composition of the present invention measured by preheating the resin composition of the present invention at 380 ℃ under a load of 5000g for 5 minutes in accordance with ASTM D1238 and measuring the melt flow rate.

The ratio r2/r1 is 1.60 or less. The ratio r2/r1 is more preferably 1.50 or less, and still more preferably 1.47 or less, for the reason that tensile elongation at break, impact resistance, toughness, flexibility, and low dielectric property are more excellent.

The fluorocopolymer (II) dispersed in the form of particles is larger than r2/r1 when the fluorocopolymer (II) is coagulated and the particles of the fluorocopolymer (II) are coarsened by the MFR measurement. Therefore, the ratio r2/r1 of 1.60 or less means that the particles of the fluorocopolymer (II) are less likely to agglomerate in the MFR measurement.

In the resin composition of the present invention, the average dispersed particle diameter of the fluorocopolymer (II) is preferably 2.5 μm or less. By setting the average dispersed particle diameter to 2.5 μm or less, a molded article having more excellent tensile elongation at break, impact resistance, toughness, flexibility and low dielectric constant can be produced.

The average dispersed particle diameter of the fluorocopolymer (II) is more preferably 2.0 μm or less, and still more preferably 1.5 μm or less, for the reason that a molded article having higher properties can be obtained and moldability is more excellent. The lower limit of the average dispersed particle diameter is not particularly limited, and may be 0.01. mu.m.

In the resin composition of the present invention, the maximum dispersion particle diameter of the fluorocopolymer (II) is preferably 5 μm or less. When the maximum dispersion particle diameter is 5 μm or less, tensile elongation at break, impact resistance, toughness, flexibility and low dielectric constant property are improved. When the maximum dispersion particle diameter is 3 μm or less, a molded article having more excellent tensile elongation at break, impact resistance, toughness, flexibility and low dielectric constant property can be produced. The lower limit of the maximum dispersion particle size is not particularly limited, and may be 0.01. mu.m.

In the resin composition of the present invention, the average dispersed particle diameter and the maximum dispersed particle diameter of the fluorocopolymer (II) are determined in accordance with the following procedures.

The average dispersed particle diameter of the fluorocopolymer in the resin composition can be confirmed as follows: the average dispersed particle size was confirmed by cutting a chip cut from the strand or pellet of the resin composition perpendicularly to the extrusion direction and using a confocal laser microscope for the cross section. The obtained microscope Image was analyzed using Image analysis software (Image J). The diameter of the equivalent circle is determined by selecting the dispersed phase. The equivalent circle diameters of 20 dispersed phases were calculated and averaged to obtain an average dispersed particle diameter.

The aromatic polyether ketone resin (I) is not particularly limited as long as it contains a repeating unit composed of an arylene group, an ether group [ -O- ] and a carbonyl group [ -C (═ O) - ], and contains a repeating unit represented by any one of the following formulae (a1) to (a5), for example.

[-Ar-O-Ar-C(＝O)-] (a1)

[-Ar-O-Ar-C(＝O)-Ar-C(＝O)-] (a2)

[-Ar-O-Ar-O-Ar-C(＝O)-] (a3)

[-Ar-O-Ar-C(＝O)-Ar-O-Ar-C(＝O)-Ar-C(＝O)-] (a4)

[-Ar-O-Ar-O-Ar-C(＝O)-Ar-C(＝O)-] (a5)

(wherein Ar represents a 2-valent aromatic hydrocarbon ring group which may or may not have a substituent)

Examples of the 2-valent aromatic hydrocarbon ring group represented by Ar include arylene groups having 6 to 10 carbon atoms such as phenylene (o-phenylene, m-phenylene, p-phenylene, etc.), naphthylene, etc., bisarylene groups (each arylene group having 6 to 10 carbon atoms), such as biphenylene (2,2 ' -biphenylene, 3 ' -biphenylene, 4 ' -biphenylene, etc.), etc., and triarylene groups (each arylene group having 6 to 10 carbon atoms), such as o-triphenylene, m-triphenylene, p-triphenylene, etc. These aromatic hydrocarbon ring groups may have a substituent such as a halogen atom, an alkyl group (e.g., a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group), a haloalkyl group, a hydroxyl group, an alkoxy group (e.g., a linear or branched alkoxy group having 1 to 4 carbon atoms such as a methoxy group), a mercapto group, an alkylthio group, a carboxyl group, a sulfo group, an amino group, an N-substituted amino group, or a cyano group. In the repeating units (a1) to (a5), the types of Ar may be the same or different from each other.

Preferred Ar's are phenylene (e.g., p-phenylene), biphenylene (e.g., 4' -biphenylene).

Examples of the resin having the repeating unit (a1) include polyether ketones (for example, "PEEK-HT" manufactured by Victrex). Examples of the resin having the repeating unit (a2) include polyetherketoneketone (for example, "PEKK" manufactured by Arkema + Oxford Performance Material). Examples of the resin having the repeating unit (a3) include polyetheretherketone (for example, "Victrex PEEK" manufactured by Victrex, "Vestakeep (registered trademark)" manufactured by Evonik, and "Vestakeep-J" manufactured by Daicel Evonik, "ketsphere (registered trademark)" manufactured by Solvay Speciality Polymers), and polydiphenyl ether-phenyl ketone (for example, "Kadel (registered trademark)" manufactured by Solvay Speciality Polymers). Examples of the resin having the repeating unit (a4) include polyetherketoneetherketoneketone (for example, "Victrex ST" manufactured by Victrex corporation). Examples of the resin having the repeating unit (a5) include polyetheretherketon and the like.

In the repeating unit composed of an arylene group, an ether group and a carbonyl group, the ratio of the ether segment (E) to the ketone segment (K) is, for example, 0.5 to 3, preferably about 1 to 2.5, as an E/K ratio. Since the ether chain imparts flexibility and the ketone chain imparts rigidity to the molecular chain, the more the ether chain, the faster the crystallization rate, and the higher the crystallinity that can be finally achieved, and the more the ketone chain, the higher the glass transition temperature and the higher the melting point tend to be.

These aromatic polyether ketone resins (I) may be used alone or in combination of two or more.

Among these aromatic polyether ketone resins (I), aromatic polyether ketone resins having any of the repeating units (a1) to (a4) are preferable. For example, the aromatic polyether ketone resin (I) is preferably at least one resin selected from the group consisting of polyether ketone, polyether ether ketone, polyether ketone, and polyether ketone ether ketone. Still more preferably at least one resin selected from the group consisting of polyetherketone, polyetheretherketone and polyetherketoneketone. In particular, polyetherketoneketone is preferable because a molded article having more excellent tensile elongation at break, impact resistance, toughness, flexibility, and low dielectric constant can be produced.

The Melt Flow Rate (MFR) of the aromatic polyether ketone resin (I) measured at 380 ℃ under a load of 5000g is preferably 1 to 150g/10 min, more preferably 5 to 130g/10 min, and still more preferably 10 to 100g/10 min. By setting the MFR within the above range, a molded article having further excellent tensile strength can be obtained.

The MFR of the aromatic polyether ketone resin (I) is measured by using a melt flow index meter according to ASTM D1238.

The aromatic polyether ketone resin (I) is present at 60sec^-1Excellent melt viscosity at 390 ℃ and excellentIs selected to be 0.01 to 4.0kNsm^-2. When the melt viscosity is in the above range, the processability is improved, and a molded article having excellent tensile strength can be obtained. A preferred lower limit of the melt viscosity is 0.05kNsm^-2More preferably 0.10kNsm^-2More preferably 0.15kNsm^-2. A preferred upper limit of the melt viscosity is 2.5kNsm^-2More preferably 1.5kNsm^-2More preferably 1.0kNsm^-2。

The melt viscosity of the aromatic polyether ketone resin (I) was measured in accordance with ASTM D3835-02.

The glass transition temperature of the aromatic polyether ketone resin (I) is preferably 130 ℃ or higher. More preferably 135 ℃ or higher, and still more preferably 140 ℃ or higher. By setting the glass transition temperature within the above range, a resin composition having excellent heat resistance can be obtained. The upper limit of the glass transition temperature is not particularly limited, but is preferably 220 ℃ or lower, more preferably 180 ℃ or lower from the viewpoint of moldability.

The glass transition temperature was measured under measurement conditions including a temperature rise rate of 20 ℃/min using a Differential Scanning Calorimetry (DSC) apparatus in accordance with JIS K7121.

The melting point of the aromatic polyether ketone resin (I) is preferably 300 ℃ or higher. More preferably 320 ℃ or higher. When the melting point is within the above range, the heat resistance of the obtained molded article can be improved. Further, the melting point is preferably 380 ℃ or lower, and when an aromatic polyether ketone resin having a melting point of at least this range is kneaded, the thermal deterioration of the fluorocopolymer during kneading may be severe, and the physical properties may not be maintained.

The melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ℃/minute using a Differential Scanning Calorimetry (DSC) apparatus.

The fluorocopolymer (II) is, for example, a polymer having at least one polymerized unit based on a fluorine-containing ethylenic monomer. The fluorine-containing copolymer (II) is preferably a melt-processable fluororesin. The fluorocopolymer (II) may be used in 1 kind or 2 or more kinds.

Examples of the fluorinated copolymer (II) include Tetrafluoroethylene (TFE)/Hexafluoropropylene (HFP) copolymer, TFE/HFP/perfluoro (alkyl vinyl ether) (PAVE) copolymer, TFE/PAVE copolymer [ PFA ], ethylene (Et)/TFE copolymer, Et/TFE/HFP copolymer, polychlorotrifluoroethylene [ PCTFE ], Chlorotrifluoroethylene (CTFE)/TFE copolymer, CTFE/TFE/PAVE copolymer, Et/CTFE copolymer, TFE/vinylidene fluoride (VdF) copolymer, VdF/HFP/TFE copolymer, VdF/HFP copolymer, polyvinylidene fluoride (PVdF), and polyvinyl fluoride (PVF). Further, as long as it is a melt-processable material, Polytetrafluoroethylene (PTFE) having a low molecular weight may be used.

The PAVE is preferably a PAVE having an alkyl group having 1 to 6 carbon atoms, and examples thereof include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), and perfluoro (butyl vinyl ether).

The fluorocopolymer (II) is more preferably Tetrafluoroethylene (TFE) and a copolymer represented by the following general formula (1):

CF₂＝CF-Rf¹ (1)

(wherein Rf¹represents-CF₃or-ORf²。Rf²A perfluoroalkyl group having 1 to 5 carbon atoms). Rf above¹is-ORf²In the case of (2), the above Rf is preferred²Is a perfluoroalkyl group having 1 to 3 carbon atoms. By using the fluorocopolymer (II), a molded article excellent in tensile properties, flexibility, impact resistance and low dielectric constant can be obtained. The excellent tensile properties mean a large tensile elongation at break.

The perfluoroethylenic unsaturated compound represented by the general formula (1) is preferably at least one selected from the group consisting of Hexafluoropropylene (HFP), perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE), and more preferably at least one selected from the group consisting of hexafluoropropylene and perfluoro (propyl vinyl ether), for the reason that a molded article having more excellent tensile elongation at break, impact resistance, flexibility and low dielectric constant can be obtained.

The fluorocopolymer (II) is more preferably at least one selected from the group consisting of a copolymer of TFE and HFP, a copolymer of TFE, HFP and PPVE, and a copolymer of TFE and PPVE, and particularly preferably at least one selected from the group consisting of a copolymer of TFE and HFP, and a copolymer of TFE, HFP and PPVE.

The fluorinated copolymer (II) preferably comprises 98 to 75 mass% of polymerized units based on TFE (TFE units) relative to the total polymerized units, and 2 to 25 mass% of a perfluoroethylenic unsaturated compound represented by the general formula (1). The lower limit of the TFE content in the fluorocopolymer (II) is more preferably 77 mass%, still more preferably 80 mass%, particularly preferably 83 mass%, and particularly more preferably 85 mass%. The upper limit of the TFE content in the fluorocopolymer (II) is more preferably 97 mass%, still more preferably 95 mass%, and particularly more preferably 92 mass%.

The lower limit of the content of the perfluoroethylenically unsaturated compound represented by the general formula (1) constituting the fluorocopolymer (II) is more preferably 3% by mass, and still more preferably 5% by mass. The upper limit of the content of the perfluoroethylenically unsaturated compound represented by the general formula (1) constituting the fluorocopolymer (II) is more preferably 23 mass%, still more preferably 20 mass%, particularly preferably 17 mass%, and particularly more preferably 15 mass%.

The fluorocopolymer (II) is preferably a copolymer composed only of TFE and a perfluoroethylenic compound represented by the general formula (1).

The above fluorocopolymer (II) is polymerized at 60sec^-1The melt viscosity at 390 ℃ is preferably 0.2 to 4.0kNsm^-2. When the melt viscosity is in the above range, the processability is improved, and a molded article having further excellent tensile elongation at break, impact resistance, toughness, flexibility and low dielectric constant can be obtained. A more preferred lower limit of the melt viscosity is 0.25kNsm^-2More preferably 0.3kNsm^-2Particularly preferably 0.35kNsm^-2Most preferably 0.4kNsm^-2. A more preferred upper limit of the melt viscosity is 3.7kNsm^-2More preferably 3.6kNsm^-2Particularly preferably 3.5kNsm^-2。

The melt viscosity of the fluorocopolymer (II) was measured in accordance with ASTM D3835-02.

The Melt Flow Rate (MFR) of the fluorocopolymer (II) measured at 380 ℃ under a load of 5000g is preferably 0.1 to 100g/10 min, more preferably 0.5 to 80g/10 min, and still more preferably 0.5 to 70g/10 min. When the MFR is within the above range, a molded article having further excellent tensile elongation at break, impact resistance, toughness, flexibility, and low dielectric constant can be obtained.

The MFR of the fluorocopolymer (II) is measured in accordance with ASTM D1238 using a melt flow index meter.

The melting point of the fluorocopolymer (II) is not particularly limited, but the fluorocopolymer (II) is preferably melted at a temperature at which the aromatic polyether ketone resin (I) used in molding melts during molding, and therefore the melting point of the fluorocopolymer (II) is preferably not higher than the melting point of the aromatic polyether ketone resin (I). For example, the melting point of the fluorocopolymer (II) is preferably 200 to 323 ℃, more preferably 220 to 320 ℃, and still more preferably 240 to 315 ℃. The melting point of the fluororesin (II) was determined as the temperature corresponding to the maximum value in the heat of fusion curve at a temperature rise of 10 ℃/min using a Differential Scanning Calorimetry (DSC) apparatus.

The fluorine-containing copolymer (II) may be treated with fluorine gas or ammonia by a known method.

In the resin composition of the present invention, a reactive functional group-containing fluorocopolymer can be used because the coagulation/coalescence of the fluorocopolymer phase is easily suppressed and the rate of change in the dispersed particle diameter is easily controlled to a desired range. The reactive functional group is not particularly limited, and specifically, there may be exemplified a vinyl group, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, an aldehyde group, a carbonyldioxy group, a haloformyl group, an alkoxycarbonyl group, an amino group, a hydroxyl group, a styryl group, a methacryl group, an acryloyl group, a ureido group, a mercapto group, a thioether group, an isocyanate group, a hydrolyzable silyl group, and the like, and among them, at least one selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride group, an amino group, and a hydroxyl group is preferable, and at least one selected from the group consisting of a carboxyl group and an acid anhydride group is more preferable. These reactive functional groups may also contain two or more species. The reactive functional group may be introduced into either the end of the main chain or the side chain of the fluorocopolymer.

The amount of the functional group of the fluorocopolymer having the reactive functional group is not particularly limited, but is preferably in the range of 0.01 to 15 mol% from the viewpoint of sufficient reaction and deterioration of fluidity.

In the resin composition of the present invention, the melt viscosity ratio (I)/(II) (aromatic polyether ketone resin (I)/fluorocopolymer (II)) of the aromatic polyether ketone resin (I) to the fluorocopolymer (II)) is preferably 0.01 to 5.0. By setting the melt viscosity ratio (I)/(II) to the above range, a molded article having more excellent tensile elongation at break, impact resistance, toughness, flexibility and low dielectric constant can be obtained. The lower limit of the melt viscosity ratio (I)/(II) is more preferably 0.02, still more preferably 0.025, and particularly preferably 0.03. The upper limit of the melt viscosity ratio (I)/(II) is more preferably 4.0, still more preferably 3.0, particularly preferably 2.5, particularly preferably 2.0, and most preferably 1.8.

In the resin composition of the present invention, the mass ratio (I) of the aromatic polyether ketone resin (I) to the fluorine-containing copolymer (II) is: the ratio (II) is not particularly limited, but is preferably 99:1 to 30:70, for example. More preferably 95:5 to 35:65, and still more preferably 95:5 to 40: 60.

The Melt Flow Rate (MFR) of the resin composition of the present invention at 380 ℃ is preferably 0.1 to 100g/10 min, more preferably 1 to 80g/10 min. The resin composition having MFR within the above range is more excellent in flowability. When the MFR is less than the above range, moldability may be deteriorated. When the MFR is larger than the above range, the desired performance may not be exhibited. The MFR is a value measured under the conditions of a preheating time of 5 minutes, a temperature of 380 ℃ and a load of 5kg in accordance with ASTM D1238.

The resin composition of the present invention preferably has a relative dielectric constant of 2.60 or less. More preferably 2.58 or less, and still more preferably 2.55 or less. By setting the relative dielectric constant to be less than the above range, a resin composition having a low dielectric loss, which has been difficult to achieve in the past, can be obtained. The lower limit of the relative permittivity is not particularly limited, but is more preferably 2.30 or more. When the relative permittivity is less than 2.30, the mechanical properties are more remarkably reduced when the composition ratio of the fluorocopolymer is increased, and it becomes more difficult to obtain desired mechanical properties.

The relative dielectric constant is a value measured by a cavity resonator perturbation method.

In the resin composition of the present invention, one of the following embodiments is preferable: the ratio r2/r1 of the average dispersed particle diameter r1 of the fluorine-containing copolymer (II) to the average dispersed particle diameter r2 of the fluorine-containing copolymer (II) measured by preheating at 380 ℃ under a load of 5000g for 5 minutes in accordance with ASTM D1238 is 1.60 or less, and the aromatic polyether ketone resin (I) is PEKK.

The resin composition of the present invention may contain components other than the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) as required. The components other than the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) are not particularly limited, and fibrous reinforcing materials such as whiskers such as potassium titanate, glass fibers, asbestos fibers, carbon fibers, ceramic fibers, potassium titanate fibers, aramid fibers, and other high-strength fibers; inorganic fillers such as talc, mica, clay, carbon powder, graphite, artificial graphite, natural graphite, and glass beads; a colorant; inorganic or organic fillers generally used such as flame retardants; lubricants such as silicone oil and molybdenum disulfide; a pigment; conductive agents such as carbon black; impact resistance improvers such as rubbers; lubricants such as magnesium stearate; ultraviolet absorbers such as benzotriazole compounds; foaming agents such as boron nitride; other additives, and the like.

These additives may be added to the raw material aromatic polyether ketone resin (I) or to the raw material fluorine-containing copolymer (II) within a range not to impair the effects of the present invention. In addition, the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) may be added to the raw materials in a molten state by a side-feeding method or the like in kneading them within a range not to impair the effects of the present invention.

Fibrous Filler (III)

The resin composition of the present invention preferably further contains a fibrous filler (III). Examples of the fibrous filler used in the resin composition of the present invention include fibrous inorganic fillers such as glass fibers, carbon fibers, milled carbon fibers, metal fibers, asbestos, rock wool, ceramic fibers, slag fibers, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, xonotlite, palygorskite (attapulgite), and sepiolite, fibrous heat-resistant organic fillers typified by heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzothiazole fibers, and fibrous fillers obtained by surface-coating these fillers with a dissimilar material such as a metal or a metal oxide. Examples of the filler having a surface coated with a different material include metal-coated glass fibers and metal-coated carbon fibers. The method of coating the surface of the dissimilar material is not particularly limited, and examples thereof include various known plating methods (e.g., electrolytic plating, electroless plating, and melt plating), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, and plasma CVD), PVD, and sputtering. Among these fibrous fillers, at least one selected from the group consisting of glass fibers, carbon fibers, milled carbon fibers and aramid fibers is preferable, and at least one selected from the group consisting of glass fibers and carbon fibers is more preferable.

In the fibrous filler, the fiber diameter is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 18 μm, and still more preferably 15 μm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm, and still more preferably 6 μm. The fiber diameter referred to herein is an index average fiber diameter. The number average fiber diameter is a value calculated as follows: the number average fiber diameter was calculated from the image obtained by observing the residue obtained by dissolving the molded article in a solvent or decomposing a resin with a basic compound and the ashed residue obtained by ashing the molded article in a crucible under a scanning electron microscope.

When the fibrous filler used in the resin composition of the present invention is glass fiber, the glass composition of the glass fiber is not particularly limited, and various glass compositions represented by a glass, C glass, E glass, and the like can be used. The glass filler may contain TiO as required₂、SO₃And P₂O₅And the like. Among these, E glass (alkali-free glass) is more preferable. From the viewpoint of improving mechanical strength, the glass fiber is preferably surface-treated with a known surface treatment agent, for example, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. Further, it is preferable to perform a bundling treatment with an olefin-based resin, a styrene-based resin, an acrylic resin, a polyester-based resin, an epoxy-based resin, a urethane-based resin, or the like, and particularly preferable are an epoxy-based resin and a urethane-based resin from the viewpoint of mechanical strength. The amount of the sizing agent attached to the glass fiber after sizing treatment is preferably 0.1 to 3 mass%, more preferably 0.2 to 1 mass% of 100 mass% of the glass fiber. As the fibrous filler used in the resin composition of the present invention, flat cross-section glass fibers may be used. The flat-section glass fiber is a glass fiber having a fiber section with an average value of the major axis of preferably 10 to 50 μm, more preferably 15 to 40 μm, and still more preferably 20 to 35 μm, and an average value of the ratio of the major axis to the minor axis (major axis/minor axis) of preferably 1.5 to 8, more preferably 2 to 6, and still more preferably 2.5 to 5. In the case of using the flat-section glass fiber having the average value of the ratio of the long diameter to the short diameter in this range, the anisotropy is significantly improved, as compared with the case of using the non-circular-section fiber having the average value of the ratio of the long diameter to the short diameter of less than 1.5. The flat cross-sectional shape may be a non-circular cross-sectional shape other than a flat shape, such as an oval shape, a cocoon shape, a trilobal shape, or a shape similar thereto. Among them, a flat shape is preferable in terms of improvement of mechanical strength and low anisotropy. The flat-section glass fiber preferably has a ratio (aspect ratio) of the average fiber length to the average fiber diameter of 2 to 120, more preferably 2.5 to 70, and further preferably 3 to 50, and the ratio of the fiber length to the average fiber diameterIf the ratio is less than 2, the effect of improving mechanical strength may be reduced, and if the ratio of the fiber length to the average fiber diameter is more than 120, anisotropy may be increased and the appearance of the molded article may be deteriorated. The average fiber diameter of the flat-section glass fiber is a number average fiber diameter obtained by converting the flat-section shape into a perfect circle having the same area. The average fiber length refers to the number average fiber length in the resin composition of the present invention. The number average fiber length is a value calculated as follows: the residue of the filler collected by high-temperature ashing of the molded article, dissolution with a solvent, decomposition with a chemical, or the like is observed with an optical microscope, and the number average fiber length is calculated from the obtained image with an image analyzer. In addition, this value is calculated by a method including not counting fibers having a length of not more than the diameter of the fibers.

The mass ratio of the fibrous filler (III) is preferably 0 to 50 mass%, more preferably 5 to 40 mass%, and still more preferably 10 to 30 mass% with respect to the resin composition of the present invention.

(other additives)

In the resin composition of the present invention, additives used for improving the appearance of the resin composition can be advantageously used for improving the appearance of the resin composition. These additives are specifically described below.

(IV) dyes/pigments

The resin composition of the present invention can further contain various dyes and pigments to provide a molded article exhibiting various designs. Examples of the dye/pigment used in the resin composition of the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferricyanides such as prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, phthalocyanine dyes, and the like. The resin composition of the present invention can be further compounded with a metallic pigment to obtain a more favorable metallic color. Aluminum powder is suitable as the metal pigment. Further, by blending a fluorescent whitening agent and a fluorescent dye emitting light other than the fluorescent whitening agent, a more favorable design effect of producing a luminescent color can be imparted.

(V) Compound having Heat ray absorbing ability

The resin composition of the present invention may contain a compound having a heat ray absorbing ability. Examples of the compound include a phthalocyanine-based near-infrared absorbent, a metal oxide-based near-infrared absorbent such as ATO, ITO, iridium oxide, ruthenium oxide, ammonium oxide, and titanium oxide, a metal boride-based near-infrared absorbent such as lanthanum boride, cerium boride, and tungsten boride, and various metal compounds having excellent near-infrared absorbing ability such as a tungsten oxide-based near-infrared absorbent, and a carbon filler. The phthalocyanine-based near-infrared absorber is easily available, for example, as MIR-362 commercially available from Mitsui chemical Co. Examples of the carbon filler include carbon black, graphite (both natural and artificial graphite are included), fullerene, and the like, and carbon black and graphite are preferable. They may be used alone or in combination of 2 or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 part by mass, more preferably 0.0008 to 0.1 part by mass, and still more preferably 0.001 to 0.07 part by mass, per 100 parts by mass of the resin composition of the present invention. The content of the metal oxide-based near-infrared absorbent, the metal boride-based near-infrared absorbent and the carbon filler in the resin composition of the present invention is preferably in the range of 0.1 to 200ppm (mass ratio), and more preferably in the range of 0.5 to 100 ppm.

(VI) white pigment for high light reflection

The resin composition of the present invention can be provided with a light reflection effect by mixing a white pigment for high light reflection. As the white pigment, a titanium dioxide (particularly, titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable. The content of the white pigment for high light reflection is preferably 3 to 30 parts by mass, more preferably 8 to 25 parts by mass, per 100 parts by mass of the resin composition. In addition, 2 or more kinds of white pigments for high light reflection may be used in combination.

(VII) ultraviolet absorber

An ultraviolet absorber may be added to the resin composition of the present invention to impart weather resistance. Specific examples of the ultraviolet absorber include benzophenone series, such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfooxybenzophenone, 2 ' -dihydroxy-4-methoxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxy-5-sodiosuloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, and the like, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2' -carboxybenzophenone. Specific examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], 2- (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole, 2-bis (t-butyl-phenyl) benzotriazole, and mixtures thereof, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole, 2 '-methylenebis (4-cumyl-6-benzotriazolyl), 2' -p-phenylenebis (1, 3-benzoxazin-4-one) and 2- [ 2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl ] benzotriazole, tolyltriazole, and the like, And a copolymer of 2- (2' -hydroxy-5-methacryloyloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer; and a polymer having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as a copolymer of 2- (2' -hydroxy-5-acryloyloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the above monomer. With respect to the ultraviolet absorber, specifically, examples of the hydroxyphenyltriazine system include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-methoxyphenol, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-ethoxyphenol, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-propoxyphenol, and 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-butoxyphenol. Further, compounds in which the phenyl group of the above exemplified compounds is a2, 4-dimethylphenyl group, such as 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-hexyloxyphenol, can be exemplified. Specific examples of the ultraviolet absorber include cyclic imino esters such as 2,2 '-p-phenylenebis (3, 1-benzoxazin-4-one), 2' -m-phenylenebis (3, 1-benzoxazin-4-one), and 2,2 '-p, p' -diphenylenebis (3, 1-benzoxazin-4-one). Specific examples of the ultraviolet absorber include cyanoacrylates such as 1, 3-bis [ (2 ' -cyano-3 ', 3 ' -diphenylacryloyl) oxy ] -2, 2-bis [ (2-cyano-3, 3-diphenylacryloyl) oxy ] methyl) propane and 1, 3-bis [ (2-cyano-3, 3-diphenylacryloyl) oxy ] benzene. The ultraviolet absorber may be a polymer type ultraviolet absorber obtained by copolymerizing an ultraviolet absorbing monomer and/or a light stabilizing monomer with a monomer such as alkyl (meth) acrylate by adopting a structure of a radical polymerizable monomer compound. As the ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of a (meth) acrylate is preferably exemplified. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable from the viewpoint of ultraviolet absorptivity, and cyclic imino ester-based and cyanoacrylate-based are preferable from the viewpoint of heat resistance and color tone. Specifically, examples thereof include "Chemisorb 79" from Chemipro Kasei corporation and "Tinuvin 234" from BASF Japan corporation. The above ultraviolet absorbers may be used alone or in the form of a mixture of 2 or more.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 1 part by mass, still more preferably 0.05 to 1 part by mass, and particularly preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the resin composition of the present invention.

(VIII) antistatic agent

The resin composition of the present invention sometimes requires antistatic properties, and in this case, it is preferable to contain an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts typified by dodecylbenzene sulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and boric acid phosphonium salts such as tetrafluoroboric acid phosphonium salts. The content of the phosphonium salt is preferably 5 parts by mass or less, preferably 0.05 to 5 parts by mass, more preferably 1 to 3.5 parts by mass, and still more preferably 1.5 to 3 parts by mass, per 100 parts by mass of the resin composition of the present invention. Examples of the antistatic agent include (2) alkali metal (alkaline earth metal) salts of organic sulfonic acids such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. The metal salt may also be used as a flame retardant as described above. More specifically, the metal salt includes, for example, a metal salt of dodecylbenzenesulfonic acid, a metal salt of perfluoroalkanesulfonic acid, and the like. The content of the alkali metal (alkaline earth metal) salt of an organic sulfonic acid is preferably 0.5 parts by mass or less, more preferably 0.001 to 0.3 parts by mass, and still more preferably 0.005 to 0.2 parts by mass, per 100 parts by mass of the resin composition of the present invention. Particularly suitable are alkali metal salts such as potassium, cesium and rubidium.

Examples of the antistatic agent include (3) ammonium salts of organic sulfonic acids such as ammonium salts of alkylsulfonic acids and ammonium salts of arylsulfonic acids. The amount of the ammonium salt is preferably 0.05 part by mass or less based on 100 parts by mass of the resin composition of the present invention. Examples of the antistatic agent include (4) polymers containing a poly (oxyalkylene) glycol component as a constituent thereof, such as polyetheresteramide. The polymer is preferably 5 parts by mass or less based on 100 parts by mass of the resin composition of the present invention.

(IX) Filler Material

The resin composition of the present invention may contain various known fillers as reinforcing fillers other than the fibrous filler. Examples of the filler include various plate-like fillers and particulate fillers. Here, the plate-like filler is a filler having a plate-like shape (including a plate-like shape having irregularities on the surface and a plate-like shape having a curve). The particulate filler is a filler having a shape other than these, including irregular shapes.

Examples of the plate-like filler include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, graphite, and a plate-like filler obtained by coating the surface of these fillers with a different material such as a metal or a metal oxide. The particle size is preferably in the range of 0.1 to 300 μm. The region of the particle size of about 10 μm is a value based on the median diameter (D50) of the particle size distribution measured by an X-ray transmission method which is one of the liquid-phase sedimentation methods; a region of 10 to 50 μm is a value based on the median diameter (D50) of the particle size distribution measured by a laser diffraction-scattering method; in the region of 50 to 300 μm, the value is based on a vibration type screening method. The particle diameter is a particle diameter in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based ones, or may be a granulated product obtained by bundling or compressing various resins such as olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

(X) other resins or elastomers

In the resin composition of the present invention, other resins or elastomers may be used in place of a part of the resin component in a small amount within the range in which the effects of the present invention are exhibited, within the range in which the effects of the present invention are not impaired. The compounding amount of the other resin or elastomer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and most preferably 3 parts by mass or less, per 100 parts by mass of the resin composition of the present invention. Examples of the other resin include resins such as polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, and epoxy resins. Examples of the elastomer include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate/styrene/butadiene) rubber as a core-shell elastomer, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, fluororubber, and fluoroelastomer.

(XI) other additives

The resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersing agents such as liquid paraffin, photocatalyst-based antifouling agents, photochromic agents, and the like.

In the resin composition of the present invention, the total amount of the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) is preferably 100 to 50% by mass. If the amount is less than 50% by mass, the tensile elongation at break and flexibility may be lost, and desired mechanical properties may not be obtained.

The resin composition of the present invention can be produced by melt-kneading the aromatic polyether ketone resin (I) and the fluorocopolymer (II) while applying a high shear force. Specifically, the time can be increased by the time of 600 seconds^-1Melt-kneading at a shear rate of not less than (/ sec).

The present invention also provides a method for producing a resin composition, which comprises subjecting an aromatic polyether ketone resin (I) and a fluorine-containing copolymer (II) to a reaction for 600 seconds^-1And a step of kneading at the shear rate described above.

The shear rate is more preferably 700 seconds^-1(second) or more, more preferably 750 seconds^-1(second) or more, particularly preferably 800 seconds^-1(in/sec). This makes it possible to disperse the fluorocopolymer (II) in the aromatic polyether ketone resin (I) in the order of submicron order, and further to suppress the coagulation of the fluorocopolymer (II) during molding. As a result, the obtained resin composition can be made more excellent in fluidity, and a molded article excellent in tensile properties, flexibility, impact resistance and low dielectric constant can be provided.

The shear rate (γ) is a value obtained by using, for example, the following equation.

γ＝πDr/C

D: screw outer diameter (mm)

r: screw rotation speed (rpm)

C: outer diameter clearance (mm)

The melt kneading is preferably performed while applying a high shearing force to the aromatic polyether ketone resin and the fluorocopolymer. The apparatus used for the above melt kneading is not particularly limited, and the melt kneading can be carried out by a conventionally used twin-screw extruder, single-screw extruder, multi-screw extruder, tandem extruder, or roll mill as a batch kneader, torque rheometer (LABO plastics), banbury mixer, pressure kneader, or mixing mill by adjusting kneading conditions such as a special screw, a high rotation speed, and a narrow gap under which shearing can be more effectively applied. Thus, the fluorocopolymer can be dispersed in the aromatic polyether ketone resin in the order of submicron order, and the coagulation of the fluorocopolymer during molding can be suppressed. As a result, the surface of the molded article of the obtained resin composition is not peeled off, and a molded article having more excellent tensile properties, flexibility, impact resistance and low dielectric constant properties can be provided. The device capable of applying a high shear force is preferably implemented using a twin-screw extruder or a high shear processing machine (a back-flow type high shear processing machine) having an internal reciprocating screw in a kneading section.

The internal reciprocating screw is a screw having a reciprocating hole formed along a screw center axis from a front end portion toward a rear end portion. The following cycle was performed in a high shear processor having an internal reciprocating screw in the kneading section: the molten resin injected into the kneading section is fed to the tip side with the rotation of the internal reciprocating screw, flows into the reciprocating hole from the inlet port at the tip end, flows backward, is discharged from the outlet port, and is fed to the tip side again with the rotation of the internal reciprocating screw. By this circulation, the molten resin is highly dispersed and mixed, and the size of the dispersed phase can be reduced. Examples of the high shear processing machine include those described in Japanese patent application laid-open Nos. 2005-313608 and 2011-046103.

When a twin-screw extruder is used as the kneading machine, a twin-screw extruder having a screw structure with a large L/D ratio is preferably used. The screw configuration of the twin-screw extruder is preferably 30 or more in terms of L/D, more preferably 35 or more in terms of L/D, and still more preferably 40 or more in terms of L/D. L/D is the effective length (L) of the screw/the screw diameter (D). From the viewpoint of improving kneading properties and productivity, melt kneading by a twin-screw extruder is most preferable.

The time for melt kneading is preferably 1 to 600 seconds, more preferably 5 to 300 seconds. If the melt kneading time is longer than the above time, the deterioration of the resin becomes significant, and the desired performance may not be exhibited. If the melt-kneading time is shorter than the above time, dispersibility may be deteriorated, and desired performance may not be obtained.

The temperature for melt kneading is required to be not less than the melting point of the aromatic polyether ketone resin and not less than the melting point of the fluorine-containing copolymer (II), and is preferably 240 to 450 ℃, more preferably 260 to 400 ℃.

The form of the resin composition of the present invention is not particularly limited, and may be pellets. That is, pellets obtained by molding the resin composition of the present invention are also one aspect of the present invention.

The pellets of the present invention may be obtained by kneading the aromatic polyether ketone resin (I) and the fluorocopolymer (II) to obtain the resin composition of the present invention, taking the kneaded product out of a kneader, and then molding the kneaded product into the shape of pellets, or may be formed by kneading the aromatic polyether ketone resin (I) and the fluorocopolymer (II) using a kneader, and then extruding the kneaded product by melt extrusion or the like.

The molding method is not particularly limited, and examples thereof include a method of melt extrusion using a twin-screw extruder or the like.

The pellets may be molded into the shape of pellets and then added with known components that can be added later. As a method of adding the additive to the pellets, a known method can be used, and examples thereof include a method of spraying the pellets by spraying or the like, and a method of dry-mixing the pellets and the additive powder. For example, the pellets may be formed by adding a lubricant (e.g., magnesium stearate) thereto. The molded article formed from the pellets has excellent tensile elongation at break. And is excellent in impact resistance, flexibility and low dielectric constant.

The pellets may be further kneaded after adding known components that can be added later.

Further, pellets obtained by molding the resin composition obtained by the above-mentioned production method and pellets obtained by adding a lubricant after molding are also one aspect of the present invention.

The components other than the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) may be added to and mixed with the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) in advance, or may be added when the aromatic polyether ketone resin (I) and the fluorine-containing copolymer (II) are mixed.

A molded article formed from the resin composition or pellet of the present invention is also one aspect of the present invention.

The molded article made of the resin composition of the present invention can be generally obtained by injection molding the pellet. In this injection molding, not only a molding method of a general cold runner system but also a hot runner system which can be used without a runner can be used for the production. In addition, in the injection molding, not only a usual molding method but also a gas-assist injection molding, an injection extrusion molding, an ultra high-speed injection molding, an injection compression molding, a two-color molding, a sandwich molding, an in-mold coating molding, an insert molding, a foam molding (including a molding using a supercritical fluid), a rapid-heating cooling mold molding, a heat insulating mold molding, an in-mold remelting molding, a molding method using a combination thereof, and the like can be used. In addition, film molding, extrusion molding, wire molding by extrusion, tube molding, and sheet molding can be used.

The present invention also provides a molded article comprising an aromatic polyether ketone resin (I) and a fluorine-containing copolymer (II), and having a tensile elongation at break of 20% or more (hereinafter also referred to as "the 2 nd molded article of the present invention").

In the 2 nd molded article of the present invention, the tensile elongation at break is preferably 20% or more, more preferably 25% or more. Further, by using the resin composition of the present invention, the tensile elongation at break can be made 30% or more, and can also be made 40% or more. The upper limit is not limited as the tensile elongation at break is larger, and may be 200%, for example.

The tensile elongation at break is a value measured at a test speed of 2mm/min by Autograph in accordance with ASTM D638.

The Charpy strength of the 2 nd molded article of the present invention is preferably 4KJ/m²Above, more preferably 9KJ/m²The above. The upper limit is not limited as the Charpy impact strength is larger, and may be, for example, 200KJ/m²。

The Charpy strength is a value measured in accordance with ASTM D6110-02.

In the 2 nd molded article of the present invention, the number of cells peeled off in the checkerboard peeling test is preferably less than 20% of the total number of cells. When the number of the peeled lattices is less than 20%, the molded article is less likely to have surface peeling, and the tensile elongation at break can be improved to maintain other mechanical properties. And can maintain a beautiful appearance.

The checkerboard peel test was carried out by evaluating the molded article by the number of 25 squares of 1mm square peeled in accordance with JIS K5400.

In the 2 nd molded article of the present invention, the average dispersed particle diameter of the fluorocopolymer (II) is preferably 4 μm or less. The average dispersed particle diameter of the fluorocopolymer (II) is more preferably 3 μm or less, and still more preferably 2.5 μm or less, for the reason that a molded article having higher properties can be obtained and moldability is more excellent. The lower limit of the average dispersed particle diameter is not particularly limited, and may be 0.01. mu.m.

In the 2 nd molded article of the present invention, the maximum dispersed particle diameter of the fluorocopolymer (II) is preferably 10 μm or less. The maximum dispersion particle diameter of the fluorocopolymer (II) is more preferably 5 μm or less for further improving the mechanical properties. The lower limit of the maximum dispersion particle size is not particularly limited, and may be 0.01 μm or less.

In the 2 nd molded article of the present invention, the average dispersed particle diameter and the maximum dispersed particle diameter of the fluorocopolymer (II) are determined by the same procedure as in the resin composition of the present invention.

The 2 nd molded article of the present invention preferably has a relative dielectric constant of 2.60 or less. More preferably 2.58 or less, and still more preferably 2.55 or less. The relative permittivity is more preferably 2.30 or more. When the relative dielectric constant is less than 2.30, the mechanical properties are more remarkably reduced when the composition ratio of the fluorocopolymer is increased, and it is difficult to obtain desired mechanical properties.

The relative permittivity is a value measured by a cavity resonator perturbation method.

The aromatic polyether ketone resin (I) and the fluorocopolymer (II) in the molded article 2 of the present invention are the same as those described for the resin composition of the present invention.

The 2 nd molded article of the present invention can be suitably used in the same manner as the molded article formed from the resin composition or pellet of the present invention described above.

Examples

The present invention will be described with reference to examples, but the present invention is not limited to these examples.

< Melt Flow Rate (MFR) >

(1) The MFR of the fluorocopolymer was measured at 380 ℃ under a load of 5000g according to ASTM D1238 using a melt flow index meter.

(2) MFR of the aromatic polyether ketone resin was measured at 380 ℃ under a load of 5000g according to ASTM D1238 using a melt flow index meter.

(3) The MFR of the resin composition obtained by mixing the fluorocopolymer with the aromatic polyether ketone resin is a value measured under the conditions of a preheating time of 5 minutes, a temperature of 380 ℃ and a load of 5000g in accordance with ASTM D1238.

< melting Point >

The melting point of the fluorocopolymer was determined as the temperature corresponding to the maximum value in the heat of fusion curve at a temperature rise of 10 ℃/min using a Differential Scanning Calorimetry (DSC) apparatus.

The melting point of the aromatic polyether ketone resin was determined by using a Differential Scanning Calorimetry (DSC) apparatus to determine the temperature corresponding to the maximum value in the heat of fusion curve at a temperature rise of 10 ℃/min.

< glass transition temperature (Tg) >

The measurement was carried out using a Differential Scanning Calorimetry (DSC) apparatus.

< calculation of average dispersed particle diameter >

A slice was cut out from the kneaded product (resin composition) obtained in examples, the strand of MFR obtained in examples, and the injection-molded article (molded article) obtained in examples, and the slice was cut perpendicularly to the flow direction, and the cross section thereof was photographed by a confocal laser microscope, and the obtained microscopic Image was analyzed by an Image analysis software (Image J). The diameter of the equivalent circle is determined by selecting the dispersed phase. The equivalent circle diameters of 20 dispersed phases were calculated and averaged to obtain an average dispersed particle diameter r1 and an average dispersed particle diameter r 2.

< shear rate during kneading >

The shear rate (γ) during kneading was determined using the following equation.

γ＝πDr/C

D: screw outer diameter (mm)

r: screw rotation speed (rpm)

C: outer diameter clearance (mm)

< preparation of injection molded article >

The resin compositions produced in examples and comparative examples were dried at 120 ℃ for 8 hours and then injection-molded using a small injection molding machine, thereby obtaining ASTM multipurpose test pieces (127 × 12.7 × 3.2mmt) and ASTM V dumbbell test pieces.

< measurement of tensile elongation at Break >

The tensile elongation at break was measured by Autograph according to ASTM D638 using the injection molded article produced by the above method. As for the measurement conditions, it was carried out at a test speed of 2 mm/min.

< measurement of relative dielectric constant >

The strand produced in the measurement of the melt flow rate was cut into a long piece having a width of 2mm and a length of 100mm, and the relative dielectric constant at 2.45GHz was measured by a cavity resonator perturbation method (network analyzer).

< checkerboard peeling test >

The injection-molded article produced by the above method was evaluated according to JIS K5400 with respect to the number of peeled cells among 25 cells of 1mm square.

The following materials were used in examples and comparative examples.

Aromatic polyether ketone resin (1): polyetherketoneketone (MFR; 40.2g/10 min, melting point; 331 ℃, Tg; 162 ℃).

Aromatic polyether ketone resin (2): polyetherketoneketone (MFR; 79.5g/10 min, melting point; 360 ℃ C., Tg; 165 ℃ C.).

Aromatic polyether ketone resin (3): polyetheretherketone (MFR; 24.5g/10 min, melting point; 340 ℃, Tg; 143 ℃).

Aromatic polyether ketone resin (4): polyetheretherketone (MFR; 75.6g/10 min, melting point; 343 ℃, Tg; 143 ℃).

Aromatic polyether ketone resin (5): polyetheretherketone (MFR; 10.0g/10 min, melting point; 342 ℃ C., Tg; 143 ℃ C.).

Aromatic polyether ketone resin (6): polyetheretherketone (MFR; 29.6g/10 min, melting point; 340 ℃, Tg; 143 ℃).

Fluorine-containing copolymer (1): TFE/HFP/PPVE copolymer. MFR; 29.8g/10 min. Melting point; at 260 ℃.

Fluorine-containing copolymer (2): TFE/HFP/PPVE copolymer. MFR; 12.3g/10 min. Melting point; 255 ℃.

Fluorine-containing copolymer (3): TFE/PPVE copolymer. MFR; 31.4g/10 min. Melting point; 301 deg.c.

Circular cross-section chopped glass fiber (1): the fiber diameter is 10 μm, and the cutting length is 3 mm.

Example 1

Aromatic polyether ketone resin (1) and fluorine-containing copolymer (1) were dry-blended at the ratio (mass%) shown in Table 1, dried at 120 ℃ for 8 hours, and the dried product was refluxed for a high temperatureThe shear processor (manufactured by NIIGATA MACHINE TECHNO) was melt-kneaded under the following predetermined conditions. The diameter of the reciprocating hole is defined asThe processing machine of (1).

L/D of the screw: 1.8

Mixing temperature: 370 deg.C

Shear rate during kneading: 870 seconds^-1

Mixing time: 10 seconds

Examples 2 to 3

Resin compositions were prepared in the same manner as in example 1, except that the type of the aromatic polyether ketone resin and the type of the fluorine-containing copolymer were changed as shown in table 1. And various physical properties were measured in the same manner. The results are shown in Table 1.

Examples 4 to 6

Aromatic polyether ketone resin (3) and fluorocopolymer (1) were premixed in the proportions (mass%) shown in Table 1, and a twin-screw extruder (b) was usedL/D-36) was added to the above mixture, and melt-kneaded at a cylinder temperature of 390 ℃. Using the obtained resin composition, various physical properties were measured in the same manner as in example 1. The results are shown in Table 1.

Example 7

The aromatic polyether ketone resin (1), the fluorine-containing copolymer (1) and the chopped glass fibers (1) were dry-blended at the proportions (mass%) shown in table 2, dried at 120 ℃ for 8 hours, and the dried product was melt-kneaded under the following predetermined conditions using a reflux high shear processing machine (manufactured by NIIGATA MACHINE TECHNO). Using reciprocating holes having a diameter ofThe processing machine of (1).

L/D of the screw: 1.8

Mixing temperature: 370 deg.C

Shear rate during kneading: 870 seconds^-1

Mixing time: 10 seconds

Comparative examples 1 to 3

Except that the kind of the aromatic polyether ketone resin and the kind of the fluorocopolymer were changed as shown in Table 1, and the twin-screw extruder was changed toA resin composition was produced in the same manner as in example 1, except that the L/D was 60. And various physical properties were measured in the same manner. The results are shown in Table 1.

Comparative example 4

Resin compositions were produced in the same manner as in example 1 except that the kind of the aromatic polyether ketone resin and the kind of the fluorine-containing copolymer were changed as shown in table 1 and a torque rheometer (LABO plastics) was used instead of the twin-screw extruder. And various physical properties were measured in the same manner. The results are shown in Table 1.

Comparative examples 5 and 6

A resin composition was produced in the same manner as in comparative example 3, except that the kind of the aromatic polyether ketone resin and the kind of the fluorine-containing copolymer were changed as shown in table 1. And various physical properties were measured in the same manner. The results are shown in Table 1.

Comparative example 7

Aromatic polyether ketone resin (1), fluorine-containing copolymer (1) and chopped glass fiber (1) were dry-blended at the ratios (mass%) shown in table 2, and dried at 120 ℃ for 8 hours to obtain a dried product, and the twin-screw extruder was changed to oneA resin composition was produced in the same manner as in example 7, except that L/D was 60. And various physical properties were measured in the same manner. The results are shown in Table 2.

[ Table 2]