JP2011213894A - Composition, pellet, resin molded product and electric cable, and method for manufacturing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing a fluoropolymer, superior in heat resistance even if a small amount of an additive for improving its own heat resistance is added.SOLUTION: The composition is characterized by including: a fluoropolymer (A); and a tetrapyrrole-based cyclic compound (B) (except a cobalt compound).

Description

The present invention relates to a composition and pellets that can be suitably used for continuous use at high temperatures, and particularly suitable for forming a coating material for electric wires, a resin molded article, and an electric wire. It also relates to a method for producing the composition.

Fluorine-containing polymers are used in various molded products such as electronic devices, vehicles, and other electric wires, and these molded products may be exposed to high temperatures not only under production but also under use. Therefore, the fluoropolymer used as a raw material is required to have heat stability at high temperatures and heat aging resistance.

Under such circumstances, for the purpose of improving the heat resistance of the fluorine-containing polymer, it has been proposed to add an additive to the composition for producing a molded article. For example, Patent Document 1 discloses an ethylene-4 fluoroethylene copolymer composition with improved thermal stability obtained by adding and mixing copper or a copper compound to an ethylene-4 fluoroethylene copolymer. ing.

By the way, in patent document 2, in the fluorine-type grease aiming at the deterioration phenomenon under high temperature conditions, being excellent in heat resistance, and being stable in the long term, fluorosilicone oil (I), Disclosed is a heat-resistant grease composition containing a fluororesin thickener (b) and at least one additive (c) represented by a modified undecane mixture, modified butane, Cu phthalocyanine, Ca sulfonate, etc. Yes.

Patent Document 3 describes that, in a heat-resistant resin product including a resin layer in which particulate matter is dispersed, the effect of reducing carbon dioxide can be obtained by including a metal porphyrin complex in the liposome as the particulate matter. Has been.

Japanese Patent Laid-Open No. 52-25850 Japanese Patent Laid-Open No. 8-143883 JP 2007-204666 A

However, when adding copper or copper oxide as in Patent Document 1, it is necessary to use a relatively large amount of additives to improve heat resistance, and the heat resistance of the fluorine-containing polymer is superior to that of the fluorine-containing polymer. It is desirable to improve without impairing the above.

Patent Document 3 describes that by including a metal porphyrin complex in an outer shell material such as a liposome, a carbon dioxide reduction effect can be obtained at the time of incineration. This metal porphyrin complex contributes to an improvement in heat resistance. That is not described at all. In addition, as described above, when a metal porphyrin ring is included in the outer shell material, the metal porphyrin ring and the oxygen radical that causes thermal degradation or the radical of the main chain attacked by the oxygen radical are sufficient. Since no interaction is obtained and electrons cannot be transferred, the effect of improving heat resistance cannot be obtained.

An object of the present invention is to provide a composition containing a fluorine-containing polymer, which is excellent in heat resistance even when an additive for improving heat resistance is added in a small amount.

The inventors of the present invention have studied various means for improving heat resistance, and adding a tetrapyrrole-based cyclic compound to the fluorine-containing polymer exerts a special effect on improving heat resistance, and the addition amount is small. Has also found that heat resistance can be improved, and has completed the present invention.

That is, this invention is a composition characterized by including a fluorine-containing polymer (A) and a tetrapyrrole-type cyclic compound (B) (however, except a cobalt compound).

The tetrapyrrole-based cyclic compound (B) preferably has a content of 1 to 100 ppm with respect to the fluoropolymer (A).

The tetrapyrrole cyclic compound (B) preferably has a porphyrin ring or a phthalocyanine ring.

The tetrapyrrole cyclic compound (B) preferably has a porphyrin ring.

The tetrapyrrole-based cyclic compound (B) is preferably an organometallic complex in which a ligand having a porphyrin ring or a phthalocyanine ring is coordinated to a metal atom.

The metal atom is preferably at least one selected from the group consisting of copper, zinc, manganese, nickel, and iron.

It is also one of the preferable embodiments that the metal atom is at least one selected from the group consisting of zinc, manganese, nickel, and iron.

It is one of the preferable forms that the metal atom is copper or zinc.

It is preferable that the composition further contains a titanium oxide.

The fluorine-containing polymer (A) includes at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, perfluoro (alkyl vinyl ether), chlorotrifluoroethylene, vinylidene fluoride, and vinyl fluoride. It is preferred to include polymerized units based on it.

The fluoropolymer (A) is composed of polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / tetra Fluoroethylene / hexafluoropropylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride A group consisting of a polymer, a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer, a vinylidene fluoride / hexafluoropropylene copolymer, and polyvinyl fluoride. It is preferably at least one selected.

The fluorine-containing polymer (A) is preferably at least one selected from the group consisting of an ethylene / tetrafluoroethylene copolymer and an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer.

The present invention is also a pellet characterized by comprising the above composition.

The present invention is also a resin molded product obtained by molding the above composition.

This invention is also an electric wire which has a core wire and the coating | covering material formed by coat | covering the said composition on the said core wire.

In the present invention, a fluorine-containing polymer (A) and a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) are mixed, and the fluorine-containing polymer (A) and the fluorine-containing polymer (A) are mixed. And a step of obtaining a master batch for resin molding containing a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) exceeding 0.1% by mass, And a step of obtaining the composition by adding the polymer (A).
The present invention is described in detail below.

The composition of the present invention contains a fluorine-containing polymer (A) and a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound). By including the tetrapyrrole-based cyclic compound (B) and the fluorine-containing polymer (A), it has excellent heat resistance. For example, when the composition of the present invention is heated, excellent heat resistance is obtained even if the amount of the tetrapyrrole-based cyclic compound (B) is small, so there is no need to add a large amount of additives. It is possible to prevent the deterioration of the mechanical strength of the molded product formed from the above. Moreover, since the outstanding heat resistance is acquired even if the addition amount of the said tetrapyrrole-type cyclic compound (B) is small, discoloration resulting from a metal atom can be suppressed. Furthermore, for example, when copper iodide or copper chloride is added, iodine or chlorine is generated, which may adversely affect the surroundings, but the tetrapyrrole-based cyclic compound (B) does not have that fear. The “cobalt compound” is a compound containing cobalt, and includes, for example, an organometallic complex in which a ligand is coordinated to a cobalt atom. Hereinafter, when referred to as “tetrapyrrole cyclic compound (B)” in the present specification, it means a tetrapyrrole cyclic compound having no cobalt atom.

In the present specification, the tetrapyrrole-based cyclic compound (B) is a compound having a structure in which four pyrrole rings are cyclically bonded. Examples of the tetrapyrrole-based cyclic compound (B) include compounds having a structure in which each of the four pyrrole rings is cyclically bonded with one carbon atom or one nitrogen atom in between, and more specifically, porphyrin A compound having a ring, a phthalocyanine ring or the like is mentioned as a preferred compound.

The tetrapyrrole-based cyclic compound (B) may be an organometallic complex in which a ligand having a structure in which four pyrrole rings are bonded in a ring is coordinated to a metal atom (excluding a cobalt atom). However, it may be one that does not have a metal atom, but the organometallic complex is more preferable from the viewpoints of stability and durability of the effect. The composition of the present invention can further improve the heat resistance of a molded product obtained from the composition and prevent thermal degradation by including an organometallic complex composed of a ligand having a specific structure and a metal atom. it can. The metal atom of the organometallic complex is preferably at least one selected from the group consisting of copper, zinc, manganese, nickel, and iron. By adding an organometallic complex having a specific metal atom to the composition, the heat resistance of the composition can be improved even with a small amount. The metal atom is more preferably copper or zinc. In the present specification, the “ligand” means an atomic group containing an atom coordinated to the metal atom. The metal atom of the organometallic complex is preferably at least one selected from the group consisting of zinc, manganese, nickel, and iron.

The tetrapyrrole-based cyclic compound (B) is preferably a compound having a porphyrin ring or a phthalocyanine ring, and more preferably a compound having a porphyrin ring. That is, the composition of the present invention preferably contains a fluorine-containing polymer (A) and a tetrapyrrole-based cyclic compound (B). The porphyrin ring has the following formula:

It is an organic skeleton consisting of a carbon atom and a nitrogen atom represented by The tetrapyrrole-based cyclic compound (B) may be a compound in which a substituent is bonded to the porphyrin ring.

The phthalocyanine ring has the following formula:

Is an organic skeleton composed of carbon and nitrogen. The tetrapyrrole-based cyclic compound (B) may be a compound in which a substituent is bonded to the phthalocyanine ring.

The tetrapyrrole cyclic compound (B) is preferably an organometallic complex in which a ligand having a porphyrin ring or a phthalocyanine ring is coordinated to a metal atom.

The metal atom coordinated by the ligand having a porphyrin ring or a phthalocyanine ring is preferably at least one selected from the group consisting of copper, zinc, manganese, nickel, and iron. By adding an organometallic complex having a ligand having a specific structure and a specific metal atom to the composition, the heat resistance of the composition can be improved even with a small amount. More preferably, the metal atom is copper or zinc.

As the organometallic complex in which the ligand having a porphyrin ring is coordinated to a metal atom, for example, the following formula (1):

(In formula, R < ¹ > is the same or different and represents a C1-C10 hydrocarbon group which may have a hydrogen atom or an oxygen atom. M is copper, zinc, manganese, nickel, or It is preferably a compound represented by: R ¹ may have an arylene group such as a phenylene group, an alkoxy group, or a hydroxyl group. R ¹ may be the same or different, for example, a hydrogen atom, a phenyl group, an alkylphenyl group having an alkyl group having 1 to 4 carbon atoms, an alkoxyphenyl group having an alkoxy group having 1 to 4 carbon atoms, or the number of carbon atoms It is also preferable that it is a 1-10 alkyl group. M is preferably copper or zinc.

As an organometallic complex in which a ligand having a porphyrin ring is coordinated to a metal atom, for example, the following formula (2):

(In formula, R < ² > is the same or different and represents a hydrogen atom or a C1-C4 alkyl group. M represents copper, zinc, manganese, nickel, or iron.) It is also a preferred form. R ² is more preferably a methyl group. M is preferably copper or zinc.

As an organometallic complex in which a ligand having a phthalocyanine ring is coordinated to a metal atom, for example, the following formula (3):

(In formula, R < ³ > is the same or different, and represents the C1-C10 hydrocarbon group which may have a hydrogen atom or an oxygen atom. M is copper, zinc, manganese, nickel, or It is also preferable that it is a compound represented by this. R ³ may have an arylene group such as a phenylene group, an alkoxy group, or a hydroxyl group. R ³ is the same or different, for example, a hydrogen atom, a phenyl group, an alkylphenyl group having an alkyl group having 1 to 4 carbon atoms, an alkoxyphenyl group having an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. It is also preferable that it is a C-10 alkyl group. R ³ is more preferably a hydrogen atom. M is preferably copper or zinc.

As the tetrapyrrole-based cyclic compound (B), a compound represented by the above formula (1) or a compound represented by the above formula (3) is preferable, a compound represented by the above formula (2), or The compound represented by the formula (3) is more preferable, and the compound represented by the formula (2) is more preferable.

As the tetrapyrrole-based cyclic compound (B), for example, phthalocyanine copper, phthalocyanine zinc, porphyrin copper, or porphyrin zinc is more preferable, and porphyrin copper or porphyrin zinc is more preferable.

The tetrapyrrole-based cyclic compound (B) is preferably in a mass ratio of 1 to 100 ppm with respect to the fluoropolymer (A). The content of the tetrapyrrole-based cyclic compound (B) is more preferably 80 ppm or less, and further preferably 50 ppm or less. According to the composition of the present invention, the heat resistance of the composition and a molded product obtained from the composition can be improved even when the content of the tetrapyrrole-based cyclic compound (B) is as small as 100 ppm or less. it can.

The tetrapyrrole-based cyclic compound (B) can be produced by a conventionally known method. Moreover, a commercial item can be used.

By the way, even when the tetrapyrrole cyclic compound (B) is contained in the composition, when the tetrapyrrole cyclic compound (B) is contained in the outer shell substance such as a liposome, Sufficient interaction cannot be obtained between the tetrapyrrole-based cyclic compound (B) and oxygen radicals that cause thermal degradation or radicals of the main chain generated by attacking oxygen radicals, and electrons cannot be transferred. Therefore, it is considered that the effect of improving heat resistance cannot be obtained. That is, the present invention includes a composition comprising a fluoropolymer (A) and a tetrapyrrole cyclic compound (B) (provided that the tetrapyrrole cyclic compound (B) is included in the outer shell substance such as a liposome). It is also a preferable form.

The composition of the present invention contains a fluorine-containing polymer (A). Therefore, it is excellent in heat resistance and mechanical strength. The fluorine-containing polymer (A) may be obtained by polymerizing only a fluorine-containing monomer, or by polymerizing a fluorine-containing monomer and a fluorine-free monomer having no fluorine atom. It may be. The fluoropolymer (A) may be a resin or an elastomer, but is preferably a resin when used as, for example, a wire coating.

The fluoropolymer (A) includes tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride [VF], hexafluoropropylene [HFP], and hexafluoroisobutene. [HFIB], CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10). Monomer, CF ₂ = CF-ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms) and perfluoro (alkyl vinyl ether) [PAVE], and CF ^{_{2 = CF-OCH 2 -Rf 2}} ( wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) alkyl perfluorovinyl ether derivative represented by, triflic Having polymerized units based on at least one fluorine-containing monomer selected from the group consisting of ethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and iodine-containing fluorinated vinyl ethers Is preferred. The fluorine-containing polymer (A) has a polymer unit based on at least one monomer selected from the group consisting of ethylene [Et], propylene [Pr], and alkyl vinyl ether as a fluorine-free monomer. You may do it.
The fluorine-containing polymer (A) is more preferably a copolymer containing polymerized units based on at least one monomer selected from the group consisting of TFE, HFP, PAVE, CTFE, VdF and VF. The fluorine-containing polymer (A) is preferably a copolymer having a polymerization unit based on Et as a fluorine-free monomer.

In the present specification, the “polymerized unit” means a part of the molecular structure of the fluoropolymer (A) and a part based on the corresponding monomer.

When the fluoropolymer (A) is a resin, the fluoropolymer (A) is a polytetrafluoroethylene [PTFE], a TFE / HFP copolymer [FEP], a TFE / PAVE copolymer [PFA], Et. / TFE copolymer, Et / TFE / HFP copolymer, polychlorotrifluoroethylene [PCTFE], CTFE / TFE copolymer, Et / CTFE copolymer, polyvinylidene fluoride [PVdF], TFE / VdF copolymer It is preferably at least one selected from the group consisting of a coalescence, a VdF / HFP / TFE copolymer, a VdF / HFP copolymer, and polyvinyl fluoride [PVF]. In the present specification, as described above, when “TFE / HFP copolymer” is described, a polymerization unit based on TFE (TFE unit) and a polymerization unit based on HFP (HFP unit) are included. It means that it is a copolymer containing. The same applies to other copolymers.

PTFE may be a TFE homopolymer or a modified PTFE. In the present specification, the above-mentioned “modified PTFE” means a product obtained by copolymerizing a small amount of a comonomer (modifier) with TFE so as not to impart melt processability to the obtained copolymer.

The modifier in the modified PTFE is not particularly limited as long as it can be copolymerized with TFE. For example, HFP and other perfluoroolefins; CTFE and other chlorofluoroolefins; trifluoroethylene and VdF and other hydrogen-containing materials Perfluorovinyl ether; perfluoroalkylethylene such as perfluorobutylethylene; ethylene and the like. Moreover, 1 type may be sufficient as the modifier used, and multiple types may be sufficient as it.

It does not specifically limit as perfluoro vinyl ether used as a modifier, For example, following general formula (I):
_{CF 2 = CF-ORf (I} )
(Wherein Rf represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.

As the perfluorovinyl ether used as the modifier, for example, perfluoro (alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (I) is preferable. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

In the modified PTFE, the proportion (mass%) of the modifier in the total amount of the modifier and TFE is usually preferably 1% by mass or less, and more preferably 0.001 to 1% by mass.

In the FEP, the HFP unit is more than 2% by mass, preferably 20% by mass or less, and more preferably 10 to 15% by mass.

As PAVE in said PFA, what has a C1-C6 alkyl group is preferable, and PMVE, PEVE, or PPVE is more preferable. The PFA has a PAVE unit of more than 2% by mass and preferably 5% by mass or less, and more preferably 2.5 to 4.0% by mass.

The FEP or PFA may be further polymerized with other monomers as long as it has the above-described composition. Examples of the other monomer include PAVE in the case of the FEP, and HFP in the case of the PFA. The said other monomer can use 1 type (s) or 2 or more types.

The other monomer to be polymerized with the FEP or PFA varies depending on the type, but it is usually preferably 1% by mass or less of the mass of the fluoropolymer (A). A more preferred upper limit is 0.5% by mass, and a still more preferred upper limit is 0.3% by mass.

The Et / TFE copolymer preferably has an Et unit: TFE unit molar ratio of 20:80 to 80:20. When the Et unit content is less than 20:80, productivity may be poor, and when the Et unit content exceeds 80:20, corrosion resistance may be deteriorated. More preferably, the molar ratio of Et units: TFE units is 35:65 to 55:45. The Et / TFE copolymer is a copolymer including a polymerized unit based on TFE and a polymerized unit based on Et, and may have a polymerized unit based on another fluorine-containing monomer.

The Et / TFE copolymer is at least one selected from the group consisting of other fluorine-containing monomers and monomers containing no fluorine in addition to Et units and TFE units as a monomer component. It is also one of the preferable forms that it has a monomer unit based on a seed monomer. The other fluorine-containing monomer is not particularly limited as long as it can be added to both ethylene and TFE, but a fluorine-containing vinyl monomer having 3 to 10 carbon atoms is easy to use. For example, hexafluoroisobutylene, _{CH 2 = CFC 3 F 6 H} , HFP and the like. Among them, the following general formula:
CH ₂ = CH-Rf ⁴
A fluorine-containing vinyl monomer represented by the formula (wherein Rf ⁴ represents a perfluoroalkyl group having 4 to 8 carbon atoms) is also one preferred form. Moreover, as a monomer which does not contain fluorine at all, the following general formula:
CH ₂ = ^{CH-R 4}
(In the formula, R ⁴ is not particularly limited in carbon number, and may contain an aromatic ring, and may contain a carbonyl group, an ester group, an ether group, an amide group, a cyano group, a hydroxyl group, or an epoxy group. R ⁴ may not be fluorine.
In addition, the Et / TFE copolymer is an Et / TFE / HFP copolymer (EFEP), which is one of the preferred embodiments. Furthermore, other fluorine-containing monomers (excluding HFP), or You may have a monomer unit based on the monomer which does not contain a fluorine at all. The monomer other than ethylene and TFE is preferably 10 mol% or less, and more preferably 5 mol% or less of the total monomer component of the copolymer composed of ethylene and TFE. Et unit: TFE unit: The molar ratio of monomer units based on other fluorine-containing monomers or monomers not containing fluorine at all is 31.5 to 54.7: 40.5 to 64. 7: It is preferable that it is 0.5-10.

The above-mentioned PCTFE is a polymer whose polymer units are substantially composed only of CTFE units.

In the CTFE / TFE copolymer, the molar ratio of CTFE units to TFE units is preferably CTFE: TFE = 2: 98 to 98: 2, more preferably 5:95 to 90:10, More preferably, it is 20: 80-90: 10.

The CTFE / TFE copolymer is preferably a copolymer comprising CTFE, TFE, and a monomer copolymerizable with CTFE and TFE. Monomers copolymerizable with CTFE and TFE include ethylene, VdF, HFP, CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, n is an integer of from 1 to 10.) the monomer represented by, PAVE, _{and, CF 2 = CF-OCH 2} -Rf 3 ( wherein, Rf ³ is a perfluoroalkyl of 1 to 5 carbon atoms An alkyl perfluorovinyl ether derivative represented by the following formula :), among which at least one selected from the group consisting of ethylene, VdF, HFP and PAVE is preferable, and it is PAVE. More preferred. Examples of PAVE include those described above. The molar ratio of CTFE units, TFE units, and monomer units copolymerizable with CTFE and TFE is the total monomer units of CTFE units and TFE units: monomer units copolymerizable with CTFE and TFE = It is preferable that it is 90-99.9: 10-0.1.

In the Et / CTFE copolymer, the molar ratio of Et units to CTFE units is preferably CTFE: Et = 30: 70 to 70:30, and more preferably 40:60 to 60:40.

The PVdF is a polymer whose polymerization units are substantially composed only of VdF units.

The VdF / HFP copolymer preferably has a VdF / HFP molar ratio of 45 to 85/55 to 15, more preferably 50 to 80/50 to 20, and still more preferably 60 to 80/40. ~ 20. The VdF / HFP copolymer is a copolymer including a polymer unit based on VdF and a polymer unit based on HFP, and may have a polymer unit based on another fluorine-containing monomer. For example, VdF / HFP / TFE copolymer is also a preferred form.

As the VdF / HFP / TFE copolymer, a VdF / HFP / TFE molar ratio of 40 to 80/10 to 35/10 to 25 is preferable. The VdF / HFP / TFE copolymer may be a resin or an elastomer, but is usually a resin when having the above composition range.

The PVF is a polymer whose polymer units are substantially composed of only VF units.

The fluoropolymer (A) is at least selected from the group consisting of an Et / TFE copolymer and an Et / TFE / HFP copolymer from the viewpoint of excellent heat resistance, chemical resistance, weather resistance, gas barrier properties, and the like. More preferably, it is one. The Et / TFE copolymer and the Et / TFE / HFP copolymer, when heated for a long time in the vicinity of the melting point, cause thermal deterioration, become colored, become brittle or foam, but the composition of the present invention. Since it contains the tetrapyrrole-based cyclic compound (B), the heat resistance is improved.

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

When the fluoropolymer (A) is a resin, the melting point of the fluoropolymer (A) is preferably 150 to 270 ° C., for example, depending on the use of the composition. In addition, when the fluoropolymer (A) has a melting point, the fluoropolymer (A) is a resin.
In the present specification, the melting point of the fluorine-containing polymer (A) was determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised at a rate of 10 ° C./min using a DSC apparatus (manufactured by Seiko). Is.

Although the said fluorine-containing polymer (A) is based also on the use etc. of the composition obtained, it is preferable that a melt flow rate (MFR) is 1-60 g / 10min. The MFR is more preferably 40 g / 10 minutes or less. If the MFR is too large, the mechanical strength may not be sufficient.

The fluoropolymer (A) can have a melt flow rate within the above-mentioned range by adjusting the copolymer composition and molecular weight. In the present specification, the melt flow rate is a value measured at a temperature of 372 ° C. and a load of 5 kg according to ASTM D3307-01 when the fluoropolymer (A) is PFA or FEP. When the fluoropolymer (A) is neither PFA nor FEP, it is a value measured at a temperature of 297 ° C. and a load of 5 kg according to ASTM D3159.

When the fluoropolymer (A) is a fluoroelastomer, the fluoropolymer (A) is a VdF / HFP copolymer, a VdF / HFP / TFE copolymer, a VdF / CTFE copolymer, a VdF / CTFE / TFE copolymer, VdF / PAVE copolymer, VdF / TFE / PAVE copolymer, VdF / HFP / PAVE copolymer, VdF / HFP / TFE / PAVE copolymer, VdF / TFE / Pr copolymer and It is preferably at least one selected from the group consisting of VdF / Et / HFP copolymer, and in particular, VdF / HFP copolymer, VdF / HFP / TFE copolymer, VdF / PAVE copolymer, VdF / TFE / PAVE copolymer, VdF / HFP / PAVE copolymer and VdF / HFP / TFE / PAVE copolymer It is preferably at least one selected.

When the fluoropolymer (A) is a fluoroelastomer, the PAVE is preferably at least one monomer selected from the group consisting of perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), Perfluoro (methyl vinyl ether) is particularly preferable.

Further, the number average molecular weight Mn of the fluorine-containing elastomer is preferably 1,000 to 300,000, and more preferably 10,000 to 200,000. When the number average molecular weight is less than 1,000, the viscosity tends to be too low and the handleability tends to deteriorate. When the number average molecular weight exceeds 300,000, the viscosity tends to increase and the handleability tends to deteriorate.

The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the fluorine-containing elastomer is preferably 1.3 or more, and more preferably 1.5 or more. The upper limit of the molecular weight distribution is not particularly limited, but is preferably 8 or less. If the molecular weight distribution is less than 1.3, there is no problem in terms of physical properties, but the roll processability tends to deteriorate. If the molecular weight distribution exceeds 8, there is a tendency for heat generation during the roll process and adhesion to the roll to occur. . The weight average molecular weight Mw and the number average molecular weight Mn are obtained by GPC measurement using a solvent such as tetrahydrofuran or n-methylpyrrolidone.

The Mooney viscosity of the fluorine-containing elastomer is not particularly limited because the optimum viscosity is selected according to the molding method. For example, in the case of injection molding, the Mooney viscosity at 100 ° C. is 10 to 120, preferably 20 to 80. If it is too high, there is a tendency to cause defects such as poor molding due to poor fluidity, and too low to easily incorporate bubbles. Mooney viscosity can be measured under the following conditions in accordance with ASTM-D1646 and JIS K6300.
Measuring instrument: MV2000E rotor manufactured by ALPHA TECHNOLOGIES Inc .: 2 rpm
Measurement temperature: 100 ° C

The composition of the present invention may contain two or more fluorine-containing polymers. For example, the fluoropolymer (A) may contain an Et / TFE copolymer and FEP, an Et / TFE copolymer and PFA, or an Et / TFE copolymer. A coalescence, PFA and FEP may be contained.

The fluoropolymer (A) is preferably a polymer having a methylene group, for example, at least one selected from the group consisting of an Et / TFE copolymer, a TFE / VdF copolymer, and PVdF. It is more preferable that the polymer is.

In the composition of the present invention, the content of the fluoropolymer (A) is preferably 70% by mass or more. 80 mass% or more may be sufficient and 90 mass% or more may be sufficient. The composition of the present invention may contain an additive as necessary in addition to the fluorine-containing polymer (A) and the tetrapyrrole-based cyclic compound (B). The additive is not particularly limited. For example, when used for wire coating, flame retardant, stabilizer, ultraviolet absorber, light stabilizer, antistatic agent, nucleating agent, lubricant, filler, dispersant, metal inertness And additives such as an agent, a neutralizing agent, a processing aid, a release agent, a foaming agent, and a coloring agent. In particular, a colorant is generally added to the wire coating for identification, and titanium oxides such as titanium dioxide (TiO ₂ ) and titanium trioxide (TiO ₃ ) can be used. The composition of the present invention preferably further contains a titanium oxide.

Titanium dioxide (TiO ₂ ) is widely used as a white pigment and as a base pigment for promoting the development of other colors, and titanium dioxide (TiO ₂ ) and titanium trioxide (TiO ₃ ) Although it is also used as a photocatalyst for sterilization and soil decomposition, there has been a problem that due to the catalytic action, the resin is deteriorated by irradiation with light or by heating in air. In the case of titanium dioxide used as a pigment, this problem has been solved to some extent by the surface treatment, but the effect of the surface treatment is not so great at high temperatures, which has been a major cause of promoting resin degradation. In addition, in the case of titanium dioxide and titanium trioxide used as a photocatalyst, since surface treatment was not performed, resin degradation could not be avoided. However, the composition of the present invention is excellent in heat resistance, and has excellent heat resistance even when it contains a titanium oxide such as titanium dioxide or titanium trioxide. That is, the composition of the present invention is a particularly useful composition when it contains titanium oxide.

When the composition of this invention contains a titanium oxide, it is preferable that a titanium oxide is 1-60 mass% with respect to the total mass of a composition. Moreover, it is also preferable that it is 10-60 mass%.

Since the composition of the present invention has excellent heat resistance, it is suitable as a composition for a coating material such as an electric wire. The present invention is also a coating material comprising the above composition.

The production method of the composition of the present invention is not particularly limited, and examples thereof include conventionally known methods. For example, the fluorine-containing polymer (A) as disclosed in JP-A-63-270740 A method of dry-mixing powder obtained by compressing into a sheet with a roll, pulverizing and classifying with a pulverizer, with an organometallic complex and additives such as a colorant and a conductivity-imparting agent used as necessary Etc.

As a method for producing the composition, the fluorine-containing polymer (A), the tetrapyrrole-based cyclic compound (B), and, if necessary, an additive or the like are previously mixed in a mixer, and then a kneader, After melt-kneading with a melt extruder or the like, a method of pulverizing and classifying as necessary may be used. The composition of the present invention is one of preferred forms that is melt-kneaded. By melt-kneading, the fluorine-containing polymer (A) and the tetrapyrrole cyclic compound (B) are sufficiently mixed, and electrons are efficiently transferred between the tetrapyrrole cyclic compounds (B). Therefore, the heat resistance is further improved.
The melt-kneading is preferably performed at a temperature 20 to 60 ° C. higher than the melting point and lower than the lower one of the decomposition temperature of the fluoropolymer (A) and the decomposition temperature of the tetrapyrrole cyclic compound (B), It is more preferable to carry out at a temperature of 300 ° C. or lower.

In the present invention, the fluorine-containing polymer (A) and the tetrapyrrole-based cyclic compound (B) (excluding the cobalt compound) are mixed, and the fluorine-containing polymer (A) and the fluorine-containing polymer (A) are mixed. On the other hand, a step of obtaining a resin molding masterbatch containing tetrapyrrole-based cyclic compound (B) exceeding 0.1% by mass (excluding a cobalt compound), and the obtained resin molding masterbatch, And a step of obtaining the composition by adding the fluoropolymer (A).
A method for mixing the fluoropolymer (A) and the tetrapyrrole-based cyclic compound (B) (excluding the cobalt compound) to obtain the resin molding master batch is not particularly limited, and is a resin molding master. Conventional methods for producing batches can be used.
The step of obtaining the composition includes, for example, mixing the resin molding masterbatch, the fluorine-containing polymer (A), and additives as necessary with a mixer in advance, and then using a kneader, a melt extruder, or the like. After melt-kneading, it can be carried out by pulverizing and classifying as necessary. The temperature for melt kneading is the same as above.

The resin-molding masterbatch for producing the composition contains a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) in an amount of more than 0.1% by mass relative to the fluoropolymer (A). It is preferable. It is more preferable that the master batch for resin molding contains a tetrapyrrole-based cyclic compound (B) exceeding 0.25% by mass with respect to the fluoropolymer (A), and 0.5% with respect to the fluoropolymer (A). It is more preferable that the tetrapyrrole-type cyclic compound (B) exceeding mass% is included. The upper limit of the content of the tetrapyrrole cyclic compound (B) contained in the resin molding masterbatch is, for example, 90% by mass with respect to the fluoropolymer (A).
In addition to the fluoropolymer (A) and the tetrapyrrole-based cyclic compound (B), the resin molding masterbatch may contain the above-described additives as necessary. Examples of the additives include flame retardants, stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, nucleating agents, lubricants, fillers, dispersants, metal deactivators, neutralizing agents, processing aids, Additives such as a mold release agent, a foaming agent, and a coloring agent are listed. The present invention includes a fluorine-containing polymer (A) and a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) exceeding 0.1% by mass with respect to the fluorine-containing polymer (A). It is also a master batch for resin molding characterized by this. The composition obtained by the above production method preferably has a tetrapyrrole cyclic compound (B) content of 1 to 100 ppm. The content of the tetrapyrrole-based cyclic compound (B) is more preferably 80 ppm or less, and further preferably 50 ppm or less.

Since the composition of the present invention has excellent heat resistance, it is suitable as a composition for a coating material such as an electric wire.

The present invention is also a pellet made of the above composition. The pellet of this invention can be manufactured by the method etc. which are shown below, for example. The composition is melted in a cylinder of an extruder, and the melted fluoropolymer (A) is extruded through a die provided in the extruder. After the extruded fluoropolymer (A) strand is cooled, it is cut to a desired length, or the molten resin at the moment of exiting the die is cooled with water or air so as to follow the die surface. It can manufacture by cutting with the cutter arrange | positioned in.

The shape of the composition put into the extruder is not particularly limited, and may be a powder. In the pellet of the present invention, the content of the fluoropolymer (A) is preferably 70% by mass or more. 80 mass% or more may be sufficient and 90 mass% or more may be sufficient.

As the extruder, a uniaxial or biaxial screw extruder can be used. The melting temperature is preferably not less than the melting point of the fluoropolymer (A) and not more than the thermal decomposition temperature. A porous die can be used as the die, and the porous die is provided with a plurality of holes having a size for obtaining a desired diameter. Since the pellet of the present invention has excellent heat resistance, it is suitable as a material for a covering material such as an electric wire.

This invention is also an electric wire characterized by having a core wire and the coating | covering material formed by coat | covering the said composition on a core wire.

Since the electric wire of the present invention has a coating material composed of the above composition, it has excellent heat resistance, for example, excellent mechanical properties such as tensile properties even after heating.

In the electric wire of the present invention, the covering material preferably has a thickness of 10 to 500 μm. More preferably, it is 10-300 micrometers.

The coating material may be formed by applying a coating composition comprising the above composition on a core wire and baking it, or by forming from the composition by melt extrusion molding. It is more preferable that it is formed by melt extrusion molding.

In the case where the coating material is formed by applying a paint comprising the composition on the core wire and firing it, the firing conditions may be appropriately set depending on the type of the fluorine-containing polymer (A) to be used. For example, the firing is preferably performed at 120 to 260 ° C.

When the coating material is formed by melt extrusion molding, the melt extrusion molding conditions may be appropriately set depending on the type of the fluorine-containing polymer (A) used, for example, at 250 to 410 ° C. Is preferred.

The electric wire of the present invention may be heated after the covering material is formed. The heating may be performed at a temperature near the melting point of the fluororesin.

Although it does not specifically limit as a material of the core wire in the electric wire of this invention, The material of metal conductors, such as copper and silver, can be used.

The wire of the present invention preferably has a core wire size of 50 to 2500 μm in diameter. The covering material for the electric wire is not particularly limited as long as it is made of the composition of the present invention, but the fluoropolymer (A) in the composition of the present invention is particularly preferably an Et / TFE copolymer. The melting point of the fluoropolymer (A) is also preferably 200 to 250 ° C.

The electric wire of the present invention may be formed by forming another layer around the covering material, or by covering the other layer around the core wire and further forming the covering material around the other layer. It may be.

The other layer is not particularly limited, and may be a resin layer made of a polyolefin resin such as polyethylene [PE] or a resin such as polyvinyl chloride [PVC] in terms of cost. The thickness of the other layer is not particularly limited, and can be 25 to 500 μm.

Examples of the electric wire of the present invention include a cable and a wire. Examples of the electric wire of the present invention include a coaxial cable, a high frequency cable, a flat cable, and a heat resistant cable.

The present invention is also a resin molded product obtained by molding the above composition. The resin molded product may be formed by molding the pellet or master batch. Examples of the resin molded product include films and sheets for solar cells used as various coating materials such as transparent surface coating materials and back coating materials provided on the light incident side surface of photovoltaic elements of solar cells. Although it is mentioned, it is not specifically limited, It can use suitably for the use as which heat resistance is calculated | required.

Since the composition of the present invention has the above-described configuration, it can be excellent in heat resistance even when a small amount of additive is added. Therefore, it can utilize suitably for the use which requires heat resistance. Since the pellet of this invention consists of the said composition, it has the outstanding heat resistance. Since the electric wire of the present invention is provided with a coating material composed of the above composition, it has excellent heat resistance and excellent mechanical properties such as tensile properties even after heating.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Each numerical value of the examples was measured by the following method.

[MFR]
In accordance with ASTM D3159, using a melt indexer (manufactured by Toyo Seiki Co., Ltd.), the mass of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm under a load of 297 ° C. and 5 kg (g / 10 minutes) ) Was designated as MFR.

[Copolymer composition]
The content of each monomer unit in the copolymer was calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

[Melting point]
It calculated | required as temperature corresponding to the maximum value in the heat of fusion curve when it heated up at a speed | rate of 10 degree-C / min using DSC apparatus (made by Seiko).

[Pyrolysis temperature]
Using a differential heat / thermogravimetry apparatus (TG / DTA6200 manufactured by SII Nanotechnology Co., Ltd.), the weight change of the sample was measured while raising the temperature in air at a rate of 10 ° C./min. The temperature at which the temperature decreased by 1% was taken as the thermal decomposition temperature.

[Heat aging test]
After the kneaded resin composition is finely cut, it is put into a 120φ mold, set in a press machine set at 320 ° C., preheated for 20 minutes, and then compression molded at 4.7 MPaG for 1 minute to obtain a thickness of 1 A 5 mm sheet was obtained. A dumbbell mold conforming to ASTM D3159 was punched out from the obtained sheet, placed in a hot air circulating electric furnace maintained at 240 ° C., and left for 300 hours. This was taken out and allowed to cool, and then a tensile test was performed at a speed of 50.00 mm / min with a Tensilon universal testing machine (manufactured by ORIENTEC). Tensile strength and tensile elongation were obtained as average values when N number = 4, and the residual rate was calculated from the values before heat aging.

[Synthesis Example 1]
Distilled water (416 L) was charged into an autoclave with an internal volume of 1000 L and sufficiently purged with nitrogen. Then, 287 kg of octafluorocyclobutane was charged, and the system was maintained at 35 ° C. and a stirring speed of 130 rpm. Thereafter, 76.1 kg of tetrafluoroethylene, 2.4 kg of ethylene, 1.47 kg of (perfluorohexyl) ethylene, and 0.63 kg of cyclohexane were charged, and then 3.1 kg of di-n-propyl peroxydicarbonate was added. Polymerization was started. Since the internal pressure decreased with the progress of polymerization, a mixed gas of tetrafluoroethylene / ethylene = 57.0 / 43.0 mol% was continuously supplied to maintain the internal pressure at 1.20 MPaG. At the same time, a total amount of 18.2 kg of (perfluorohexyl) ethylene was continuously charged and polymerization was continued. 2.5 hours after the start of polymerization, 330 g of cyclohexane was added for MFR adjustment, 17 hours after the start of polymerization, the pressure was released to return to atmospheric pressure, the reaction product was washed with water and dried to obtain a fluororesin powder (fluororesin powder). 250 kg of (1)) was obtained. The polymerization rate from the start of the polymerization to 2.5 hours later was substantially constant 17.2 kg / hr, and thereafter, the polymerization rate was 16.0 kg / hr. The obtained fluororesin powder had an ethylene: tetrafluoroethylene: (perfluorohexyl) ethylene molar ratio of 42.2: 56.4: 1.4, a melting point of 252 ° C., and an MFR of 4.7 (g / 10 minutes).

[Melting and kneading]
A lab plast mill mixer (manufactured by Toyo Seiki Co., Ltd.) set at 290 ° C. is charged with 66 g of a fluororesin containing an additive having a predetermined concentration, and after pre-kneading for 10 rpm-4 minutes, it is melt-kneaded for 70 rpm-5 minutes. And a resin composition was obtained.

[Example 1]
To the fluororesin powder (1), phthalocyanine copper (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: cyanine blue) was added in a proportion of 50 mass ppm, and the mixture was shaken and mixed in a plastic bag. This mixture was melt kneaded according to the procedure described above to obtain a resin composition. The heat aging test was conducted according to the procedure described above. The results are shown in Table 1.

[Examples 2 to 8]
As additives for the fluororesin powder (1), phthalocyanine zinc, phthalocyanine, 5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphine (abbreviation: TMP) (above, Tokyo Chemical Industry Co., Ltd.) Manufactured); meso-tetra (4-methoxyphenyl) porphine copper (abbreviation: TMP-Cu), meso-tetra (4-methoxyphenyl) porphine zinc (abbreviation: TMP-Zn), octaethylporphine copper, octaethylporphine zinc (The above is manufactured by Frontier Scientific); and a resin composition was obtained in the same procedure as in Example 1 except that each was used, and then a heat aging test was performed. The results are shown in Table 1.

[Comparative Example 1]
A heat aging test was performed on the fluororesin powder (1) by the procedure described above. The results are shown in Table 1.

The composition and pellets of the present invention can be used in various applications that require heat resistance, and are particularly useful as, for example, a coating material for electric wires.

Claims (16)

A fluorine-containing polymer (A), a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound),
The composition characterized by including. The composition according to claim 1, wherein the tetrapyrrole-based cyclic compound (B) has a content of 1 to 100 ppm with respect to the fluoropolymer (A). The composition according to claim 1 or 2, wherein the tetrapyrrole-based cyclic compound (B) has a porphyrin ring or a phthalocyanine ring. The composition according to claim 1, 2 or 3, wherein the tetrapyrrole-based cyclic compound (B) has a porphyrin ring. The composition according to claim 1, 2, or 3, wherein the tetrapyrrole-based cyclic compound (B) is an organometallic complex in which a ligand having a porphyrin ring or a phthalocyanine ring is coordinated to a metal atom. The composition according to claim 5, wherein the metal atom is at least one selected from the group consisting of copper, zinc, manganese, nickel, and iron. The composition according to claim 5 or 6, wherein the metal atom is at least one selected from the group consisting of zinc, manganese, nickel, and iron. The composition according to claim 5 or 6, wherein the metal atom is copper or zinc. Furthermore, the composition of Claim 1, 2, 3, 4, 5, 6, 7 or 8 containing a titanium oxide. The fluorine-containing polymer (A) includes at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, perfluoro (alkyl vinyl ether), chlorotrifluoroethylene, vinylidene fluoride, and vinyl fluoride. A composition according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 comprising polymerized units based thereon. The fluoropolymer (A) is composed of polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, ethylene / tetra Fluoroethylene / hexafluoropropylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride A group consisting of a polymer, a vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer, a vinylidene fluoride / hexafluoropropylene copolymer, and polyvinyl fluoride. Claim 6, 7, 8, 9 or 10 composition, wherein at least one selected. The fluoropolymer (A) is at least one selected from the group consisting of an ethylene / tetrafluoroethylene copolymer and an ethylene / tetrafluoroethylene / hexafluoropropylene copolymer. The composition according to 5, 6, 7, 8, 9, 10 or 11. A pellet comprising the composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. A resin molded product obtained by molding the composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. It has a core wire and a covering material formed by coating the core wire with the composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. Electric wire. A fluorine-containing polymer (A) and a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) are mixed and 0.1% of the fluorine-containing polymer (A) and the fluorine-containing polymer (A) are mixed. A step of obtaining a master batch for resin molding containing a tetrapyrrole-based cyclic compound (B) (excluding a cobalt compound) exceeding mass%;
A step of adding the fluoropolymer (A) to the obtained resin molding masterbatch to obtain the composition according to claim 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. When,
A method for producing a composition, comprising: