JPH1067966A - Coated metal member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated metal member having the coating layer of a polyarylene sulfide resin which can stably and continuously be coated without causing the breakage of the resin, when continuously coated on a metal substrate by a melt extrusion method, which does not generate cracks in the coating layer, when thermally treated after coated, and which is excellent in heat resistance, freon gas resistance, flame retardancy, chemical resistance, radiation resistance, low temperature resistance, electric insulation, mechanical properties, etc. SOLUTION: This coated metal member is produced by coating a metal substrate with a polyarylene sulfide resin. Therein, the polyarylene sulfide resin has an extension viscosity of >=10,000 Pa.s at 310 deg.C and at a shear speed of 400/sec, and the heating crystallization temperature of the polyarylene sulfide resin coating layer measured by a differential scanning calorimeter is lower by >=6 deg.C than that of the non-oriented amorphous sheet of the polyarylene sulfide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin-coated metal member, and more particularly, to heat resistance, freon resistance, flame resistance, chemical resistance, radiation resistance, and the like.
The present invention relates to a polyarylene sulfide resin-coated metal member having excellent low-temperature properties, electrical insulation properties, mechanical properties, and the like. The coated metal member of the present invention includes a cable conduit for a control cable of an automobile or a ship, an inner cable for a control cable, a winding of a heat-resistant coil or a motor, a solenoid wire of a vehicle, a fringe-resistant electric wire such as a compressor, and a winding of a transformer. It is used in a wide range of fields, such as wires, radiation-resistant equipment wiring for nuclear power plants, and cables, metal rods, metal tubes, other heat-resistant wires, sheath tubes, and wires.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter, referred to as polyphenylene sulfide resin)
Polyarylene sulfide resin (hereinafter abbreviated as PAS resin) represented by PPS resin is used in a wide range of fields as an engineering plastic having excellent heat resistance, chemical resistance, flame retardancy, electrical insulation and the like. ing. Taking advantage of such excellent properties, it is expected that PAS resins will be used as coating resins for electric wires, metal rods, and the like, and specific proposals have been made. For example, JP-A-60-18
No. 5306 discloses a melt viscosity of 300 to 100,000 poise measured at 310 ° C. and a shear rate of 200 / sec.
A method has been proposed in which a PPS resin having a primary draw ratio of 10 or more when melt-extruded at 310 ° C. from a nozzle having a hole diameter of 0.5 mm and spun is melt-extruded onto a metal conductor to produce an enameled wire. ing. JP-A-62-1433
No. 07 discloses a melt index of 0.5 to 100.
There has been proposed an insulated wire formed by extruding a g / 10 min PPS resin composition onto a conductor.

However, if a PAS resin is melt-extruded onto a metal substrate such as a metal conductor to form a coating layer continuously, the resin is poor in stretchability, so that the resin is likely to be cut out and stably. It was difficult to obtain a coating. Further, when the PAS resin-coated metal member is coated and exposed to a high temperature to crystallize the resin, there is a problem that the coating layer is cracked. Generally, when a resin is continuously coated on a metal substrate by a melt extrusion method, the resin is stretched in a molten state. At this time, it is necessary that a uniform coating layer can be stably obtained without causing resin breakage. further,
Even if heat treatment is performed after coating, it is necessary that the coating layer does not crack. However, a PAS resin for metal coating having physical properties suitable for applications such as coated electric wires has not been found so far.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for continuously coating a metal substrate by a melt extrusion method without causing resin breakage. An object of the present invention is to provide a polyarylene sulfide resin-coated metal member that does not cause cracks in a coating layer when heat treatment is performed later. The object of the present invention is
Provide a coated metal member formed with a polyarylene sulfide resin coating layer having excellent heat resistance, freon resistance, flame retardancy, chemical resistance, radiation resistance, low-temperature physical properties, electrical insulation properties, mechanical properties, and the like. It is in.

The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems of the prior art, and have found that a PAS resin having a specific elongational viscosity is used, and a coating condition on a metal substrate is selected. The object is achieved by lowering the temperature-rise crystallization temperature of the PAS resin coating layer (coating) measured by a differential scanning calorimeter (DSC) by 5 ° C. or more than the temperature-rise crystallization temperature of the PAS resin press sheet. I found what I could do. In this case, the strength of the PAS resin coating layer at a strain of 10% is preferably 0.93 times or more of the yield strength. By selecting such coating conditions, when the PAS resin is crystallized by heat treatment after coating, the coating layer does not crack and the heat history under severe heat aging tests or heat treatment conditions is reduced. Even after receiving
A coating layer having an elongation of 0% or more can be obtained.

[0006] The PAS resin may be a completely linear resin, but is a branched PAS resin obtained by polymerizing an alkali metal sulfide and a dihalo aromatic compound in the presence of a trihalo aromatic compound. Is preferred. Such a coated metal member such as a coated electric wire coated with the selected PAS resin has a PAS resin coating layer having heat resistance, flame retardancy, chemical resistance, freon resistance, radiation resistance, electrical insulation, and low temperature. The PAS resin not only exhibits excellent properties inherent in PAS resin such as properties, but also has excellent properties such as flex resistance, tensile strength, flexibility, and weather resistance. The present invention has been completed based on these findings.

[0007]

According to the present invention, in a coated metal member comprising a metal substrate coated with a polyarylene sulfide resin, elongation of the polyarylene sulfide resin at 310 ° C. and a shear rate of 400 / sec. Viscosity 1
The crystallization temperature of the polyarylene sulfide resin coating layer measured by a differential scanning calorimeter is not less than 000 Pa · s, and is higher than the crystallization temperature of the non-oriented amorphous sheet of the polyarylene sulfide resin. Is also lower than 6 ° C.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The PAS resin used in the present invention comprises:
A linear resin obtained from only an alkali metal sulfide and a dihalo aromatic compound can be used, but the elongational viscosity is 1%.
Since the reaction is sufficiently high at 000 Pa · s or more, it is preferable that a branched resin obtained by allowing a small amount of a trihaloaromatic compound, which is a trifunctional monomer, to coexist when reacting an alkali metal sulfide with a dihaloaromatic compound. . However, the cross-linked resin obtained by oxidatively cross-linking (curing) a low-molecular-weight PAS resin in the presence of air generates a gel-like substance during melt stretching, and has poor processability. , Coating layer strength, adhesion to metal substrate, abrasion resistance,
Poor practicality in terms of insulation resistance and heat resistance.

[0009] The elongational viscosity of the PAS resin used in the present invention must be as large as 10,000 Pa · s or more, preferably 10,000 to 300,000 Pa · s.
s, more preferably 10,000 to 200,000 Pa
-It is s. Here, the extensional viscosity (Shear and
Elongational visibility)
Is F. N. Cogswell's method [Polym. E
ng. Sci. 12 , p. 64 (1972)], and a detailed measuring method will be described later. If the elongational viscosity of the PAS resin is too low, the molecular weight or the degree of branching of the PAS resin is insufficient, and if the coating layer is continuously formed by melt extrusion on a metal substrate, the stretchability of the resin is poor. It is easy to cause cutting and the like, and it may be difficult to obtain a stable coating. Also, PA
If the elongational viscosity of the S resin is too low, the elongation at break of the coating layer will be small, and the bending resistance and flexibility will be unsatisfactory. When crystallized, the coating layer is easily broken. PAS
If the elongational viscosity of the resin is too high, the processability may be reduced, or the bending resistance or flexibility of the coating layer may be reduced, and unless the take-up speed of the metal substrate during coating is reduced. The productivity is reduced. 310 of PAS resin
At a shear rate of 1200 / sec.
It is preferably at least 0 Pa · s.

The PAS resin can be obtained by reacting an alkali metal sulfide with a dihalo aromatic compound in a polar organic solvent according to a conventional method. In order to obtain a branched PAS resin, an alkali metal sulfide and a dihalo aromatic compound are polymerized in the presence of a trihalo aromatic compound.
The ratio of each monomer and the polymerization conditions are made appropriate. Examples of the alkali metal sulfide include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and a mixture thereof. Further, the alkali metal sulfide, in s in a reaction vessel in a conventional manner
It may be generated by itu . These alkali metal sulfides can be used in the form of hydrates, aqueous mixtures, or anhydrides. In order to react with alkali metal bisulfide and alkali metal thiosulfate present in trace amounts in alkali metal sulfide, a small amount of alkali metal hydroxide is added,
These impurities may be removed or converted to sulfide. Among them, sodium sulfide is industrially preferable because it is the cheapest.

Examples of the dihalo aromatic compound include, for example, p
Dihalobenzenes such as -dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene and p-dibromobenzene; 2,5-dichlorotoluene, 1-methoxy-2,5
Substituted dihalobenzenes such as dichlorobenzene; 1,4-
Dihalonaphthalene such as dichloronaphthalene; 4,4′-
Dihalobiphenyls such as dichlorobiphenyl and 3,3'-dichlorobiphenyl; dihalobenzoic acids such as 3,5-dichlorobenzoic acid; dihalobenzophenones such as 4,4'-dichlorobenzophenone;4,4'-dichlorodiphenylsulfone , 3,3'-dichlorodiphenylsulfone and the like; dihalophenylethers such as 4,4'-dichlorodiphenylether; and the like. Among these, dihalobenzene is preferred from the viewpoints of economy and physical properties, and p-dihalobenzene such as p-dichlorobenzene is more preferred. In particular, as the dihalo aromatic compound, a compound containing p-dihalobenzene in a proportion of preferably 70% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more is preferable.

Examples of the trihalo aromatic compound include, for example,
1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,
2,4-tribromobenzene, 1,3,5-trichlorobenzene, 1,3,5-tribromobenzene, 1,3-
Trihalobenzenes such as dichloro-5-bromobenzene;
Alkyl-substituted trihalobenzenes; mixtures thereof. Among these, 1,2,4-trihalobenzene, 1,2
3,5-Trihalobenzene and 1,2,3-trichlorobenzene are preferred.

As a method for producing a polyarylene sulfide resin, an alkali metal sulfide and a dihalo aromatic compound are subjected to a polycondensation reaction in a polar organic solvent containing water, optionally in the presence of a trihalo aromatic compound. A method can be adopted. Examples of the water include water of hydration of an alkali metal sulfide, added water, reaction water, and water of an aqueous solution of an alkali metal sulfide. Examples of the organic amide solvent include N-methylpyrrolidone, N-ethylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, dimethylimidazolidinone, tetramethylurea, and hexamethylphosphonamide And the like. Among these, N-methyl-2-pyrrolidone (NMP) is particularly preferred from the viewpoint of economy and stability.

The ratio a / b of the number of moles a of the charged dihalo-aromatic compound to the number of moles b of the charged alkali metal sulfide is usually 0.95 to 1.10, preferably 0.98 to 1.0.
8, more preferably in the range of 1.00 to 1.06. The trihaloaromatic compound is usually used in an amount of 0.0002 to 1 mol of the charged alkali metal sulfide.
It is adjusted to be in a range of 0.01 mol, preferably 0.0004 to 0.009 mol, more preferably 0.0005 to 0.007 mol, and added to the polymerization reaction system.

If the amount of the trihaloaromatic compound is less than 0.0002 mol per mol of the charged alkali metal compound, the elasticity in the molten state may not be sufficient if the molecular weight of the produced PAS resin is not sufficiently high. If the film is stretched directly from the film, the necessary orientation may not be obtained. For this reason, the toughness of the obtained coating layer decreases. Conversely, when the amount of the trihalo aromatic compound exceeds 0.01 mol, the melt viscosity and the degree of branching of the formed PAS resin also increase,
It is not preferable because resin breakage occurs at the time of coating and it becomes difficult to obtain a uniform coating continuously. The addition of the trihaloaromatic compound to the polymerization reaction system may be at the early stage or late stage of the polymerization, but in the initial stage, the addition of a small amount is more effective.

As the polymerization method, a conventionally known method can be adopted and is not particularly limited. Specific examples include, for example, 0.5 to 2.4 mol of water per mol of the charged alkali metal sulfide. 150-2
The reaction is carried out at a temperature of 35 ° C. until the conversion of the dihalo aromatic compound reaches about 50 to 98 mol%, and then 2.5 to 7.0 mol of water per mol of the charged alkali metal sulfide is added to the reaction system. And continuing the reaction by raising the temperature to a temperature of 245 to 280 ° C.
The amount of the polar organic solvent used is usually 0.2 to 2.0 kg, preferably 0.3 to 2.0 mol per mol of the alkali metal sulfide.
1.0 kg.

In order to continuously coat a metal base material using the above PAS resin, the extruder is used to extrude the resin at a temperature equal to or higher than the melting point of the resin.
After melting at a temperature preferably in the range of (melting point + 5 ° C.) to 370 ° C., more preferably in the range of (melting point + 20 ° C.) to 350 ° C., it is coated on a metal substrate by die outer coating while forming a parison. During the coating process, the coated metal body (that is, the coated metal member) is drawn at a constant speed by a pinch roller or the like, and immediately after passing through the die, a uniform coating layer is continuously formed. Next, the coated metal body is cooled in a cooling zone, and then usually wound up by a winder or the like.

In the present invention, (1) it is necessary that the heating crystallization temperature of the PAS resin coating layer measured by DSC is lower than the heating crystallization temperature of the non-oriented amorphous sheet of PAS resin by 6 ° C. or more. And (2) the strength of the PAS resin coating layer at a strain of 10% is preferably 0.93 of the yield strength.
Times or more, more preferably 0.95 times or more,
(3) The crystallinity of the PAS resin coating layer after heat treatment at a heat treatment temperature of 120 to 290 ° C. is in the range of 15 to 40%, (4) The strain of the PAS resin coating layer after heat treatment is 10% It is desirable that the strength at this time is 0.95 times or more of the yield strength, and (5) the elongation at break of the PAS resin layer after the heat treatment is 30% or more.

In the present invention, the difference (X−Y = ΔTc ₁ ) between the elevated crystallization temperature (X) of the PAS resin coating layer and the elevated crystallization temperature (Y) of the non-oriented amorphous sheet of the PAS resin is determined. It is necessary to be greater than 6 ° C., that is, ΔTc ₁ ≦ −6 ° C. If the difference is less than 6 ° C., the elongation at break of the PAS resin coating layer becomes small, and the bending resistance of the coating layer becomes small. And the flexibility is reduced. The range of ΔTc ₁ is usually −35 ° C. ≦ Δ
Tc ₁ ≦ −6 ° C., preferably −25 ° C. ≦ ΔTc ₁ ≦ −7 ° C.
It is.

The strength (B) at a strain of 10% of the PAS resin coating layer measured by a tensile test is the yield strength (A)
Is preferably 0.93 times or more (B / A ≧ 0.93), more preferably 0.95 times or more. If this ratio (B / A) is smaller than 0.93 times, (B / A
<0.93), the elongation at break of the PAS resin coating layer decreases, and the bending resistance and flexibility of the coating layer decrease. This ratio (B / A) more preferably satisfies 0.93 ≦ B / A ≦ 2, and still more preferably 0.95 ≦ B / A ≦ 1.8.

The degree of crystallinity of the PAS resin coating layer after heat treatment at a heat treatment temperature of 120 to 290 ° C. is preferably in the range of 10 to 40%. The coating layer of the present invention comprises PA
Since the S resin has a molecular chain orientation, the crystallinity is, for example, 3
Even if it is heat-treated until it becomes 0% or more, it has sufficient elongation. That is, the strength (B) at a strain of 10% of the PAS resin coating layer after the heat treatment is preferably 0.95 times or more of the yield strength (A).
The elongation at break of the S resin layer is preferably 30% or more.

On a metal substrate, P having such physical properties
As a method of forming the AS resin coating layer, there is a method of selecting an area reduction rate (R1) at the time of coating according to the elongational viscosity (λ ₄₀₀ ) of the PAS resin. Generally, the lower the elongational viscosity of the PAS resin, the higher the area withdrawal rate is set, and conversely, the higher the elongational viscosity of the PAS resin, the lower the area withdrawal rate is set. That is, the larger the molecular weight and the degree of branching, the more easily the PAS resin of the coating layer is oriented even if the area withdrawal rate is small. Here, the area withdrawal rate (R1) is a value obtained by dividing the cross-sectional area of the resin melt-extruded from the die of the extruder by the cross-sectional area of the coating layer. Taking the case of a covered electric wire as an example, the area withdrawal rate is expressed by the following equation. Area drop rate (R1) = [(die inner diameter) ² − (mandrel outer diameter) ² ] / [(covered wire outer diameter ² − (conductor outer diameter) ² ]

In the present invention, the strain of the PAS resin coating layer is 1
Since the strength (B) at 0% is preferably 0.93 times or more of the yield strength (A), the area withdrawing ratio (R1) satisfying B / A ≧ 0.93 is determined by the elongational viscosity (λ _400). It is desirable to select in relation to the above. Analysis of the experimental data of each of the following Examples and Comparative Examples revealed that the logarithmic curve conversion equation model fit well. When a PAS resin is coated on a metal substrate, the following relational expression (1) is used.
It was found that the elongational viscosity (λ ₄₀₀ ) and the area reduction rate (R1) of the PAS resin to be used should be selected so as to satisfy (2) and (3).

[0024]

(Equation 1) The meaning of each symbol in the formula is as follows. A: yield strength (MPa) of the PAS resin coating layer, B: strength (MP) at a strain of 10% of the PAS resin coating layer
a), λ ₄₀₀ : PAS at 310 ° C., shear rate 400 / sec.
Elongational viscosity of resin (Pa · s), R1: Area withdrawal rate (%) when coating with PAS resin.

To apply this formula, for example, the values of the elongational viscosity (λ ₄₀₀ ) and B / A of the PAS resin are determined, and the value of the area reduction rate (R1) satisfying those values is calculated by formula (2).
Is calculated from Equation (2) preferably satisfies B / A ≧ 0.9
5 [Equation (3)]. Good results can be obtained by coating under conditions satisfying these formulas (1) and (2) and satisfying the requirement of ΔTc ₁ ≦ −6 ° C. In the present invention, after controlling the crystallinity and mechanical properties of the coating layer and extruding the molten resin from a die of an extruder to obtain a desired coated metal body, forming a parison and coating the metal base material In addition, a heating zone can be provided as necessary before reaching the pinch roller to heat-treat the coated metal body. The heat treatment temperature of the coated metal body is usually from 120 to 29.
0 ° C., preferably 130 to 270 ° C. The heat treatment time (that is, the residence time in the heating zone) varies depending on the productivity, the coating film thickness, the take-up speed, the crystallization speed of the resin, and the crystallization temperature, and cannot be specified unconditionally.
The time is from 0.1 second to 10 minutes.

Further, in the present invention, in order to control the crystallinity and mechanical properties of the coating layer and to obtain a desired coating, the coated metal body once taken out can be subjected to a heat treatment if necessary. In this case, the heat treatment temperature of the coated metal body is
Usually 120-290 ° C, preferably 130-270 ° C
Range. Heat treatment time depends on productivity, film thickness, take-up speed, crystallization speed and crystallization temperature of resin,
Although it cannot be specified unconditionally, the time is usually from 1 second to 100 hours. When heat treatment is performed at a temperature lower than 120 ° C.,
Crystallization cannot be sufficiently performed, and dimensional stability at high temperatures or surface properties may be impaired, which is not preferable. When heat treatment is performed at a temperature exceeding 290 ° C., the surface properties may be impaired due to deformation of the coating layer. If the heat treatment time is less than 1 second, crystallization cannot be sufficiently performed, and dimensional stability or surface properties at high temperatures may be impaired, which is not preferable. On the other hand, if the heat treatment time is too long, the surface properties are impaired due to deformation of the coating layer, which is not preferable.

The crystallinity of the resin of the coating layer due to the heat treatment is:
When the orientation of the PAS resin in the coating layer is small, usually 3
0% or less, but the elongational viscosity is 10.0% or less.
By using a PAS resin of 00 Pa · or more and selecting an appropriate area reduction rate to enhance the orientation, even if the crystallinity is increased beyond 30% by heat treatment, sufficient elongation is maintained,
There is no possibility that the coating layer becomes brittle. The crystallinity of the resin of the coating layer is preferably 15 to 40%, more preferably 17 to 40%.
It is preferable to set the range to 35%.

The resin and the coated metal body of the present invention may contain a small amount of other components that can be mixed, in addition to the PAS resin, as long as the object of the present invention is not impaired. As other components, for example, silica, talc, mica, kaolin, calcium carbonate, magnesium phosphate,
Granular, powdery or scaly inorganic fillers such as glass, fluorine-based resins such as polytetrafluoroethylene, tetrafluoride / hexafluoroethylene copolymer, ethylene / tetrafluoroethylene copolymer, glass fiber, carbon fiber, mica Fibrous inorganic fillers such as ceramic fibers, silicone-based elastomers, acrylic-based elastomers, olefin-based elastomers, polyamide-based elastomers, impact-resistant agents such as fluorine-based elastomers, other thermoplastic resins,
Examples thereof include a thermosetting resin, a coupling agent, a lubricant, a release agent, a stabilizer, and a nucleating agent.

Although the PAS resin of the present invention has excellent adhesion to a metal substrate, for example, the coating layer has an appropriate stripping property with respect to the metal substrate in operation such as a coated electric wire. In the field where it is required, a small amount of release agent can be contained in the resin. Examples of the release agent include fatty acid esters such as pentaerythritol tristearate and diastearyl pentaerythritol diphosphate. By blending such a release agent, the adhesiveness between the metal base material and the resin coating layer is appropriately weakened, and a resin-coated metal member having strip properties can be obtained. The release agent is usually used at a ratio of 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin. Known stabilizers for PAS resins can be used as the stabilizer, but for stably melt-extruding the resin from a die of an extruder to coat the resin, for example, barium hydroxide is preferable. The stabilizer is used usually in a ratio of 0.1 to 3 parts by weight based on 100 parts by weight of the resin.

Examples of the metal substrate include long metal substrates such as metal conductors (metal conductors) such as electric wires, metal rods, metal tubes, and wires. The thickness of the PAS resin coating layer can be appropriately determined according to each application and desired physical properties. According to the present invention, heat resistance, freon resistance, flame retardancy, chemical resistance,
A resin-coated metal member such as a coated electric wire having a coating layer made of a PAS resin having excellent radiation resistance, low-temperature physical properties, electrical insulation properties, mechanical properties, and the like is obtained. Specific examples include cable conduits for control cables of automobiles and ships, inner cables for control cables, heat-resistant coils and motor windings, automotive solenoid lead wires, compressor Freon-resistant wires, transformer windings, nuclear power generation Required radiation-resistant equipment wiring, and coated metal members such as cables, metal rods, metal tubes, other heat-resistant wiring, sheath tubes, and wires.

[0031]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, the measuring method of various physical properties is as follows. (1) Elongational viscosity ・ Testing machine: Capillograph manufactured by Toyo Seiki Co., Ltd. ・ Measurement temperature: 310 ° C. ・ Capillary: diameter = 1 mm, length 20 mm, inflow angle 90 °, diameter = 0.3 mm, length 0.2 mm, inflow angle 1
80 degrees-Calculation of elongational viscosity: F. N. The calculation was performed assuming the Cogswell model. (2) Tensile test ・ Testing machine: Autograph AG-2000 manufactured by Shimadzu Corporation
E · Measurement temperature: 23 ° C · Distance between marked lines: 50 mm · Tensile speed: 50 mm / min · Strength was calculated by dividing the load by the cross-sectional area before the test. (3) Temperature rise crystallization temperature (Tc ₁ ) ・ Testing machine: DSC7 manufactured by Perkin-Elmer Co. ・ Temperature time profile: After holding at 30 ° C. for 3 minutes,
The temperature was raised to 200 ° C. at a temperature of 20 ° C./min. Sample Weight: 5 to 6 mg (4) to measure the density of the coating resin by crystallinity density gradient tube method, based on the crystal density 1.43 / cm ³ and amorphous density of 1.3195g / cm ^3, the volume The crystallinity was calculated from the measured density by the fraction.

Example 1 Polymer Synthesis Example 1 (Polymer P1) 373 kg of hydrous sodium sulfide (purity 46.10%) and N-methylpyrrolidone (hereinafter abbreviated as NMP) 800 k
g was charged into a titanium-clad polymerization vessel, and 142 kg of water was distilled off together with 54.4 mol of hydrogen sulfide while gradually raising the temperature to about 200 ° C. in a nitrogen gas atmosphere. Next, p-dichlorobenzene (hereinafter abbreviated as p-DCB) 320.6
kg, 0.796 kg of 1,2,4-trichlorobenzene
And a mixed solution of 274 kg of NMP and 220 ° C.
After performing the polymerization reaction for 1 hour at
The polymerization reaction was performed for an hour. Next, 76.5 kg of water was injected, and the reaction was carried out at 255 ° C. for 1 hour. Then, the temperature was lowered to 240 ° C., and the polymerization was continued for 3 hours. After cooling, the reaction mixture was sieved with a screen having a mesh size of 150 μm (100 mesh) to separate the granular polymer, washed with acetone and washed with water four times, and then dehydrated to obtain a dried polymer.

The pelletized polymer (P1) was supplied to a 44 mmφ twin-screw kneading extruder (TEX-44 manufactured by Nippon Steel Works) and the cylinder temperature was set to 300.
Kneading was carried out at a temperature of from 330C to 330C to produce pellets. The elongational viscosity (λ ₄₀₀ ) of the obtained polymer at 310 ° C. and a shear rate of 400 / sec was 33,000 Pa · s. The melt viscosity η ^* measured at 310 ° C. and a shear rate of 1200 / sec was 360 Pa · s.

Electric wire coating experiment The pellets obtained above were supplied to a tabletop twin-screw extruder (MP-2015 manufactured by Tuba Co., APV) equipped with an electric wire coating die, and coated with a conductive wire. The coating conditions were a cylinder temperature of 330 ° C., an output of 7.6 g / min, and a take-off speed of 33 m / min.
Min, area deduction rate (R1) 72, parison length 40m
m, and the pressure of air bleeding between the conducting wire and the coating film was −1 cmHg. The conductor is a soft copper wire 0.4mmφ (JIS C
3101) was used. The size of the coating die used was a mandrel tip outer diameter of 2.8 mmφ and a die inner diameter of 4.9 mmφ. The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa and the strength at a strain of 10% (B) was 5 MPa.
6 MPa (B / A = 1.02) and the maximum strength is 67
MPa and elongation at break were 250%. A lead wire was pulled out of the coated body, and the difference between the temperature-increased crystallization temperatures of the coated film and the non-oriented press sheet (non-oriented amorphous sheet) was measured. As a result, the heating crystallization temperature of the coating film was lower by 11 ° C. than the heating crystallization temperature of the non-oriented press sheet (ΔTc ₁ = −11).
° C).

After the coating was heat-treated under the conditions shown in Table 1,
A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. Table 1 shows the results.

[0036]

[Table 1]

The coating was placed in an air-circulating oven at 180 ° C.
, A heat aging test was performed under the conditions of 96 hours, and then a lead wire was extracted from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 91 MPa, the strength at a strain of 10% (B) was 94 MPa (B / A = 1.03), the maximum strength was 98 MPa, and the elongation at break was 80%. The crystallinity of the coated resin after the heat aging test was 34%.

Comparative Example 1 The same polymer (P
Using the pellets, extruder, and conductor of 1), the conductor was covered. The coating conditions were a cylinder temperature of 330 ° C., an output of 7.6 g / min, a take-up speed of 10 m / min, an area withdrawal rate (R1) of 22, a parison length of 25 mm, and a pressure reduction of air between the conductive wire and the coating film of −1 cmHg. . As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used. Coating die size is 2.8m outside diameter of mandrel tip
mφ and a die inner diameter of 4.9 mmφ were used. The outer diameter of the obtained coated body was 0.95 mmφ, and a coated body having no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa.
And the strength (B) at a strain of 10% is 51 MPa (B
/A=0.93), the maximum strength was 72 kPa, and the breaking elongation of the coating film was 310%. Remove the conductor from the sheath,
When the difference between the temperature-increased crystallization temperatures of the coating film and the non-oriented breath sheet was determined, the temperature-increased crystallization temperature of the coating film was lower by 5 ° C. than the temperature-induced crystallization temperature of the non-oriented press sheet (ΔTc _1). = −
5 ° C). The coating was placed in an air-circulating oven at 180 ° C for 9 hours.
After performing a heat aging test under the condition of 6 hours, a tensile test was performed. As a result, the maximum strength was 91 MPa and the elongation at break was 9%.
Met. The crystallinity of the coating resin after the heat aging test was measured in the same manner as in Example 1. As a result, it was 33%. This coated product has a small area pull-out rate (R1) and the molecular chain orientation of the coated film is insufficient. It was inferior in flexibility.

Example 2 The same polymer (P
Using the pellets, extruder, and conductor of 1), the conductor was covered. The coating conditions were a cylinder temperature of 330 ° C., an extrusion rate of 7.0 g / min, a take-up speed of 30 m / min, an area withdrawing ratio (R1) of 37, a parison length of 35 mm, and a pressure reduction of air between the conductor and the coating film of −1 cmHg. . As the size of the coating die, a mandrel tip outer diameter of 2.0 mmφ and a die inner diameter of 3.5 mmφ were used. Conductor is 0.4m of soft copper wire for electric wire
mφ (JIS C3101) was used. The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 54 MPa.
And the strength (B) at a strain of 10% is 54 MPa (B
/A=1.00), the maximum strength was 64 MPa, and the elongation at break was 300%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 8 ° C. below (ΔTc ₁ = −8
° C). The coating is placed in an air circulating oven at 180 ° C. for 96 hours.
After performing a heat aging test under the condition of time, a tensile test was performed. As a result, the yield strength (A) was 91 MPa, and the strength (B) at a strain of 10% was 93 MPa (B / A = 1.
03), the maximum strength was 99 MPa, and the breaking elongation was 50%. The crystallinity of the coating resin after the heat aging test was measured and was 35%.

Example 3 The same polymer (P
Using the pellets, extruder, and conductor of 1), the conductor was covered. The coating conditions were a cylinder temperature of 330 ° C., an output of 7.6 g / min, a take-up speed of 60 m / min, an area withdrawal rate (R1) of 273, a parison length of 45 mm, and a pressure reduction of air between the conductor and the coating film of −1 cmHg. . As the size of the coating die, a mandrel tip outer diameter of 4.0 mmφ and a die inner diameter of 7.0 mmφ were used. Conductor is soft copper wire 0.4 for electric wire
mmφ (JIS C3101) was used. The outer diameter of the obtained coated body was 0.53 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa.
And the strength (B) at a strain of 10% is 58 MPa (B
/A=1.05), the maximum strength was 92 MPa, and the elongation at break was 210%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. (ΔTc ₁ = −1)
2 ° C). The coating was placed in an air-circulating oven at 180 ° C for 9 hours.
After performing a heat aging test under the condition of 6 hours, a tensile test was performed. As a result, the yield strength (A) was 90 MPa, and the strength (B) at a strain of 10% was 98 MPa (B / A = 1.
09), the maximum strength was 130 MPa, and the elongation at break was 90%. The crystallinity of the coating resin after the heat aging test was measured and was 35%.

Example 4 The same polymer (P
Using the pellets, extruder, and conductor of 1), the conductor was covered. The coating conditions were a cylinder temperature of 330 ° C., an extrusion rate of 7.6 / min, a take-up speed of 33 m / min, an area withdrawal rate (R1) of 72, a parison length of 40 mm, and a pressure reduction of air between the conductor and the coating film of −1 cmHg. . As the size of the coating die, a mandrel tip outer diameter of 2.8 mmφ and a die inner diameter of 4.9 mmφ were used. Conductor is 0.4m of soft copper wire for electric wire
mφ (JIS C3101) was used. Immediately after coating, the coated body passes through a heating tank of about 3 m length heated to 280 ° C.,
After continuous heat treatment, it was taken out (heat treatment condition = 28
0 ° C / 5.5 seconds). The outer diameter of the obtained coating is 0.62.
With a diameter of mm, a coating having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 85 MPa, the strength at a strain of 10% (B) was 86 MPa (B / A = 1.01),
The maximum strength was 100 MPa and the elongation at break was 180%. The crystallinity of the coating resin was measured and found to be 12%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 10 ° C. below (ΔTc ₁ = −10 ° C.). The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 91 MPa, the strength at a strain of 10% (B) was 94 MPa (B / A = 1.03), the maximum strength was 97 MPa, and the elongation at break was 70%. When the crystallinity of the coating resin after the heat aging test was measured, 33
%Met.

Comparative Example 2 The same polymer (P
Using the pellets, extruder, and conductor of 1), the conductor was covered. The coating conditions were a cylinder temperature of 330 ° C., an extrusion rate of 7.6 g / min, a take-up speed of 20 m / min, an area withdrawal rate (R1) of 6, a parison length of 15 mm, and a pressure reduction of air between the conductor and the coating film of -2 cmHg. . As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used. Coating die size is 0.9m outside diameter of mandrel tip
mφ and a die inner diameter of 1.7 mmφ were used. The outer diameter of the obtained coated body was 0.73 mmφ, and a coated body with no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa.
And the strength (B) at a strain of 10% is 48 MPa (B
/A=0.87), the maximum strength was 60 MPa, and the elongation at break was 300%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. (ΔTc ₁ = −2).
° C). The coating is placed in an air circulating oven at 180 ° C for 96 hours.
After performing a heat aging test under the condition of time, a tensile test was performed. As a result, the maximum strength was 88 MPa, and the elongation at break was 5%.
Met. The degree of crystallinity of the coating resin after the heat aging test was measured and found to be 36%. This coating had an area withdrawing rate (R1) of 6 and ΔTc ₁ of −2 ° C., both of which were small, and the molecular chain orientation of the coating film was insufficient. As a result, the elongation after heat aging test ( Elongation at break)
It was inferior in bending resistance and flexibility.

[0043] [Example 5] polymer obtained in pelletized Synthesis Example 1 (P1) 100 parts by weight of pentaerythritol stearate (manufactured by NOF Corporation, UNISTAR H476) 3 minutes 1 part by weight in a tumbler mixer mixing After that, the mixture was supplied to a 44 mmφ twin-screw kneading extruder (TEX-44, manufactured by Nippon Steel Works) and the cylinder temperature was set
Kneading was performed at 00 ° C. to 330 ° C. to produce pellets. The elongational viscosity at a shear rate of 400 / sec of the obtained polymer was 32,500 Pa · s.

Wire Covering Experiment Using the above pellets, the same extruder as in Example 1, and a wire, a wire was coated. The coating condition was a cylinder temperature of 33.
0 ° C., extrusion rate 7.6 g / min, drawing speed 33 m / min,
Area withdrawal rate (R1) 72, parison length 40 mm,
The air was evacuated from the conducting wire to the coating film at a reduced pressure of -1 cmHg. Coating die size is 2.8m outside diameter of mandrel tip
mφ and a die inner diameter of 4.9 mmφ were used. As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used.
The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no irregularities on the surface was obtained. Remove the conductor from the sheath,
The coating film was subjected to a tensile test. As a result, yield strength (A)
Is 56 MPa, and the strength (B) at a strain of 10% is 58 MPa.
a (B / A = 1.04), maximum strength is 66MP
a, The elongation at break was 260%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 9 ° C. below (Δ
Tc ₁ = -9 ℃). Place the coating in an air-circulating oven for 1
After performing a heat aging test at 80 ° C. for 96 hours, a tensile test was performed. As a result, the yield strength (A) is 90 MPa.
And the strength (B) at a strain of 10% is 92 MPa (B
/A=1.02), the maximum strength was 103 MPa, and the elongation at break was 100%. The crystallinity of the coating resin after the heat aging test was measured and was 35%.

[0045] [Example 6] pelletizing the polymer obtained in Synthesis Example 1 (P1) 100 parts by weight of an epoxy-modified polysiloxane (manufactured by Toray Industries, Inc., SF841
1) After mixing 1 part by weight with a tumbler mixer for 3 minutes, a 44 mmφ biaxial kneading extruder (TEX- manufactured by Nippon Steel Works, Ltd.)
44), and kneaded at a cylinder temperature of 300 ° C. to 330 ° C. to produce pellets. The elongational viscosity of the obtained polymer at a shear rate of 400 / sec is 34,000
It was 0 Pa · s.

Wire Covering Experiment Using the pellets, the same extruder and the wire as in Example 1, the wire was covered. The coating condition was a cylinder temperature of 33.
0 ° C., extrusion rate 7.6 g / min, take-off speed 33 m / min,
Area withdrawal rate (R1) 72, parison length 32 mm,
The air was evacuated from the conducting wire to the coating film at a reduced pressure of -1 cmHg. Coating die size is 2.8m outside diameter of mandrel tip
mφ and a die inner diameter of 4.9 mmφ were used. As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used.
The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no irregularities on the surface was obtained. Remove the conductor from the sheath,
The coating film was subjected to a tensile test. As a result, yield strength (A)
Is 56MPa and the strength (B) at a strain of 10% is 55MPa.
a (B / A = 0.98), maximum strength is 70MP
a, The elongation at break was 260%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 9 ° C. below (Δ
Tc ₁ = -9 ℃). Place the coating in an air-circulating oven for 1
After performing a heat aging test at 80 ° C. for 96 hours, a tensile test was performed. As a result, the yield strength (A) is 90 MPa.
And the strength (B) at a strain of 10% is 92 MPa (B
/A=1.02), the maximum strength was 110 MPa, and the elongation at break was 90%. The crystallinity of the coating resin after the heat aging test was measured, and was 33%.

Example 7 Pelletization 90% by weight of the polymer (P1) obtained in Synthesis Example 1 and 10% by weight of an ethylene-tetrafluoroethyne copolymer (Aflon COP, C-88A manufactured by Asahi Glass Co., Ltd.) Mixture 10
A mixture obtained by adding 1 part by weight of γ-aminopropyltriethoxysilane (A-1100 manufactured by Nihon Unicolor Co., Ltd.) to 0 part by weight was mixed with a tumbler mixer for 3 minutes, and then mixed.
4mmφ twin screw kneading extruder (TEX-44 manufactured by Nippon Steel Works)
And kneaded at a cylinder temperature of 300 ° C. to 330 ° C. to produce pellets. The elongational viscosity of the obtained polymer at a shear rate of 400 / sec is 38,000 Pa.
-It was s.

Wire Covering Experiment Using the above pellets, the same extruder as in Example 1, and a wire, a wire was coated. The coating condition was a cylinder temperature of 33.
0 ° C., extrusion rate 7.6 g / min, take-off speed 33 m / min,
Area withdrawal rate (R1) 72, parison length 35 mm,
The air was evacuated from the conducting wire to the coating film at a reduced pressure of -1 cmHg. Coating die size is 2.8m outside diameter of mandrel tip
mφ and a die inner diameter of 4.9 mmφ were used. As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used.
The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no irregularities on the surface was obtained. Remove the conductor from the sheath,
The coating film was subjected to a tensile test. As a result, yield strength (A)
Is 48 MPa, and the strength (B) at a strain of 10% is 52 MPa.
a (B / A = 1.08), maximum strength is 62MP
a, The breaking elongation was 240%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 12 ° C. below (ΔTc ₁ = −12 ° C.). The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 8
At 1 MPa, the strength (B) at a strain of 10% is 85 MPa (B / A = 1.05), the maximum strength is 110 MPa,
The breaking elongation was 86%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%.

Example 8 Polymer Synthesis Example 2 (Polymer P2 ) 370 kg of hydrous sodium sulfide (purity 46.21%) and NM
800 kg of P was charged into a titanium-clad polymerization vessel, and the temperature was gradually increased to about 200 ° C. in a nitrogen gas atmosphere.
141 kg of water were distilled off together with the molar hydrogen sulphide. Next, a mixed solution of 317.4 kg of p-DCB, 0.79 kg of 1,2,4-trichlorobenzene and 270 kg of NMP was supplied, a polymerization reaction was performed at 220 ° C. for 1 hour, and the temperature was raised to 230 ° C. The polymerization reaction was performed for 3 hours. Next, 77 kg of water was injected, and the reaction was carried out at 255 ° C. for 1 hour. Then, the temperature was lowered to 240 ° C., and the polymerization was continued for 3 hours. After cooling, the reaction mixture is opened to 150 μm (100 mesh)
To separate the granular polymer, washed with acetone and washed with water four times each, and then dehydrated to obtain a dried polymer.

The supply pelletized above-obtained polymer (P2) 44mmφ twin-screw kneading extruder to (Japan Steel Works TEX-44), and the mixture was kneaded at a cylinder temperature of 300 ° C. to 330 ° C., to obtain a pellet did. 310 ° C., shear rate 4 of the obtained polymer
The extensional viscosity at 00 / sec was 90,000 Pa · s. The melt viscosity η ^* measured at 310 ° C. and a shear rate of 1200 / sec was 430 Pa · s.

Wire Plating Experiment The pellets obtained above were supplied to a tabletop twin-screw extruder (MP-2015, manufactured by Tuba Co., APV) equipped with a wire coating die to cover the conductor. Coating conditions were as follows: cylinder temperature 330 ° C., extrusion rate 20 g / min, take-off speed 25 mm /
Min, area withdrawal rate (R1) 21, parison length 35m
m, and the pressure of air bleeding between the conducting wire and the coating film was −1 cmHg. The conductor is a soft copper wire 0.4mmφ (JIS C
3101) was used. As the size of the coating die, a mandrel tip outer diameter of 2.8 mmφ and a die inner diameter of 4.9 mmφ were used. The outer diameter of the obtained coated body was 0.97 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa and the strength at a strain of 10% (B) was 5 MPa.
8 MPa (B / A = 1.05) and the maximum strength is 70
MPa and elongation at break were 260%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 10 ° C. below (ΔTc ₁ = −10 ° C.). The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 92 MPa, and the strength at a strain of 10% (B) was 97 MPa.
(B / A = 1.05) and the maximum strength is 115MP.
a, The elongation at break was 80%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%.

Example 9 The same polymer (P
Using the pellets, the extruder, and the conductor of 2), the conductor was covered. The coating conditions were as follows: a cylinder temperature of 330 ° C. and an output of 7
g / min, take-off speed 25 m / min, area drop-off rate (R1) 59, parison length 30 mm, air depressurization between the conductor and the coating film -2 cmHg. The size of the coating die is: mandrel tip outer diameter 2.8mmφ, die inner diameter 4.
9 mmφ was used. Conductor is soft copper wire 0.4mmφ for electric wire
(JIS C3101) was used. The outer diameter of the obtained coated body was 0.66 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa, and the strength (B) at a strain of 10% was 60 MPa (B / A =
1.09), maximum strength is 68 MPa, elongation at break is 230
%Met. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 13 ° C. (ΔTc ₁ = −13
° C). The coating is placed in an air circulating oven at 180 ° C. for 96 hours.
After performing a heat aging test under the condition of time, a tensile test was performed. As a result, the yield strength (A) was 93 MPa, and the strength (B) at a strain of 10% was 101 MPa (B / A =
1.09), maximum strength 130MPa, elongation at break 10
It was 0%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%.

Comparative Example 3 The same polymer (P
Using the pellets, the extruder, and the conductor of 2), the conductor was covered. The coating conditions were as follows: a cylinder temperature of 330 ° C. and an output of
0 g / min, take-off speed 25 m / min, area drop-off rate (R1) 7, parison length 35 mm, air depressurization between the lead wire and the coating film--1 cmHg. As the conductive wire, a soft copper wire for electric wire 0.4 mmφ (JIS C3101) was used. As the size of the coating die, a mandrel tip outer diameter of 2 mmφ and a die inner diameter of 3.5 mmφ were used. The outer diameter of the obtained coated body was 1.15 mmφ, and a coated body having no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa, and the strength (B) at a strain of 10% was 51 MPa (B / A =
0.93), maximum strength 72 MPa, elongation at break 290
%Met. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 4 ° C. below (ΔTc ₁ = −4 ° C.).
The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 91 MPa, and the strength at a strain of 10% (B) was 85 MPa (B / A = 0.93).
The maximum strength was 92 MPa, and the elongation at break was 11%. When the crystallinity of the coating resin after the heat aging test was measured, it was 3
4%. This coating has an area withdrawal rate (R
1) was 7 and ΔTc ₁ was −4 ° C., which were all small, and the molecular chain orientation of the coating film was insufficient. As a result, the elongation (elongation at break) after the heat aging test was extremely small, and It was inferior in flexibility and flexibility.

Example 10 Polymer Synthesis Example 3 (Polymer P3) 371 kg of hydrous sodium sulfide (purity 46.10%) and NM
800 kg of P was charged into a titanium clad polymerization vessel, and 142 kg of water was distilled off together with 54 mol of hydrogen sulfide while gradually raising the temperature to about 200 ° C. under a nitrogen gas atmosphere. next,
A mixed solution of 318.9 kg of p-DCB, 1.16 kg of 1,2,4-trichlorobenzene and 270 kg of NMP was supplied, and a polymerization reaction was carried out at 220 ° C. for 1 hour.
The temperature was raised to 30 ° C., and the polymerization reaction was performed for 3 hours. Next, water 7
After injecting 7 kg and reacting at 255 ° C for 1 hour,
The temperature was lowered to 40 ° C., and the polymerization was continued for 3 hours. After cooling, the reaction mixture was sieved with a screen having a mesh size of 150 μm (100 mesh) to separate the granular polymer, washed with acetone and washed with water four times, and then dehydrated to obtain a dried polymer.

[0055] pelletized above-obtained polymer (P3) 100 parts by weight of pentaerythritol stearate (manufactured by NOF Corporation, UNISTAR H476) after a 1 part by weight were mixed for 3 minutes in a tumbler mixer, 44Mmfai biaxial kneading and extruding (TEX-44 manufactured by Nippon Steel Works), cylinder temperature 300 ° C ~
Kneading was performed at 330 ° C. to produce pellets. The elongational viscosity of the obtained polymer at 310 ° C. and a shear rate of 400 / sec was 150,000 Pa · s. 310
° C, the melt viscosity η ^* measured at a shear rate of 1200 / sec is:
It was 550 Pa · s.

Wire Plating Experiment The pellets obtained above were supplied to a tabletop twin-screw extruder (MP-2015, manufactured by Tuba Co., APV) equipped with a wire coating die to cover the conductor. The coating conditions were a cylinder temperature of 340 ° C., an output of 7.6 g / min, and a take-up speed of 33 m / min.
Min, area deduction rate (R1) 37, parison length 35m
m, and the pressure of air bleeding between the conducting wire and the coating film was −1 cmHg. The conductor is a soft copper wire 0.4mmφ (JIS C
3101) was used. As the size of the coating die, a mandrel tip outer diameter of 2 mmφ and a die inner diameter of 3.5 mmφ were used. The outer diameter of the obtained coated body was 0.62 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 54 MPa, and the strength at a strain of 10% (B) was 65 MPa.
(B / A = 1.20) and the maximum strength is 110MP.
a, The elongation at break was 220%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 18 ° C. below (ΔTc ₁ = −18 ° C.). The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 9
At 0 MPa, the strength (B) at a strain of 10% is 110 MPa
(B / A = 1.22) and the maximum strength is 150MP
a, The elongation at break was 90%. The crystallinity of the coating resin after the heat aging test was measured, and was 33%.

Example 11 Using the same polymer (P3) pellets, extruder and conductive wire as in Example 10, the conductive wire was covered. The coating conditions were a cylinder temperature of 340 ° C., an extrusion rate of 9 g / min, a take-up speed of 20 m / min, an area withdrawing ratio (R1) of 19, a parison length of 20 mm, and a pressure reduction of air between the conductive wire and the coating film of -2 cmHg. The size of the coating die is as follows: the outer diameter of the mandrel tip is 2 mmφ, and the inner diameter of the die is 3.5.
mmφ was used. Conductor is soft copper wire 0.4mmφ for electric wire
(JIS C3101) was used. The outer diameter of the obtained coated body was 0.77 mmφ, and a coated body with no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 54 MPa, and the strength (B) at a strain of 10% was 62 MPa (B / A =
1.15), maximum strength is 103 MPa, elongation at break is 24
It was 0%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 14 ° C. below (ΔTc ₁ = −14
° C). The coating is placed in an air circulating oven at 180 ° C. for 96 hours.
After performing a heat aging test under the condition of time, a tensile test was performed. As a result, the yield strength (A) was 91 MPa, and the strength at a strain of 10% (B) was 106 MPa (B / A =
1.16), maximum strength 130 MPa, elongation at break 11
It was 0%. The crystallinity of the coating resin after the heat aging test was measured, and was 33%.

Example 12 Polymer Synthesis Example 4 (Polymer P4) 373 kg of hydrous sodium sulfide (purity 46.10%) and NM
800 kg of P was charged into a titanium-clad polymerization vessel, and the temperature was gradually increased to about 200 ° C. in a nitrogen gas atmosphere.
143 kg of water were distilled off along with the molar hydrogen sulfide. Next, a mixed solution of 320.7 kg of p-DCB, 0.39 kg of 1,2,4-trichlorobenzene and 266 kg of NMP was supplied, a polymerization reaction was carried out at 220 ° C. for 1 hour, and the temperature was raised to 230 ° C. The polymerization reaction was performed for 3 hours. Next, 77.5 kg of water was injected, and the reaction was carried out at 255 ° C. for 1 hour. Then, the temperature was lowered to 240 ° C., and the polymerization was continued for 3 hours.
After cooling, the reaction mixture was separated by a screen having a mesh size of 150 μm (100 mesh) to separate a granular polymer, washed with acetone and washed with water four times, and then dehydrated to obtain a dried polymer.

[0059] supplying pelletized above-obtained polymer (P4) 4 mm diameter twin-screw kneading extruder to (Japan Steel Works TEX-44), and the mixture was kneaded at a cylinder temperature of 300 ° C. to 330 ° C., to obtain a pellet did. 310 ° C., shear rate 40 of the obtained polymer
The elongational viscosity at 0 / sec was 11,100 Pa · s. The melt viscosity η ^* measured at 310 ° C. and a shear rate of 1200 / sec was 340 Pa · s.

Wire Plating Experiment The pellets obtained above were supplied to a tabletop twin-screw extruder (MP-2015, manufactured by Tubaco APV) equipped with a wire coating die, and covered with a conductive wire. The coating conditions were a cylinder temperature of 325 ° C., an extrusion rate of 8.8 g / min, and a take-up speed of 40 m / min.
Min, area deduction rate (R1) 156, parison length 50
mm, and the pressure was reduced by 1 cmHg to remove air from the conductive wire and the coating film. The conductor is a soft copper wire for wire 0.4mmφ (JIS
C3101) was used. As the size of the coating die, a mandrel tip outer diameter of 4 mmφ and a die inner diameter of 7 mmφ were used. The outer diameter of the obtained coated body was 0.6 mmφ, and a coated body having no unevenness on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) is 55
In MPa, the strength (B) at a strain of 10% was 51 MPa (B / A = 0.93), the maximum strength was 95 MPa, and the elongation at break was 300%. Remove the conductor from the sheath,
When the difference between the temperature-increased crystallization temperatures of the coating film and the non-oriented press sheet was determined, the temperature-increased crystallization temperature of the coating film was 7 ° C lower than the temperature-increased crystallization temperature of the non-oriented press sheet (ΔTc). ₁ =
-7 ° C). When this coated body was heat-treated at 150 ° C. for 96 hours, the yield strength (A) of the coated film was 88 MPa, and the strength (B) at a strain of 10% was 84 MPa (B / A =
0.95), elongation at break is 100%, crystallinity is 28%
It became. The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the yield strength (A) was 92 MPa, and the strength at a strain of 10% (B) was 91 MPa (B / A =
0.99), maximum strength 98MPa, elongation at break 43%
Met. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%.

Example 13 Using the same polymer (P4) pellets, extruder and conductor as in Example 12, the conductor was coated. The coating conditions were a cylinder temperature of 325 ° C., an extrusion rate of 8.8 g / min, a take-up speed of 80 m / min, an area withdrawing rate (R1) of 299, a parison length of 53 mm, and a pressure reduction of air between the conductor and the coating film of −1 cmHg. . As the size of the coating die, a mandrel tip outer diameter of 4 mmφ and a die inner diameter of 7 mmφ were used. Conductor is soft copper wire 0.4mm for electric wire
φ (JIS C3101) was used. The outer diameter of the obtained coated body was 0.52 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 55 MPa,
The strength (B) at a strain of 10% is 53 MPa (B / A
= 0.96), maximum strength is 97 MPa, elongation at break is 26
It was 0%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 10 ° C. below (ΔTc ₁ = −10
° C). The coating is placed in an air circulating oven at 180 ° C. for 96 hours.
After performing a heat aging test under the condition of time, a tensile test was performed. As a result, the yield strength (A) was 91 MPa, and the strength (B) at a strain of 10% was 92 MPa (B / A = 1.
01), the maximum strength was 105 MPa, and the elongation at break was 56%. The crystallinity of the coating resin after the heat aging test was measured and was 35%.

Comparative Example 4 Using the same polymer (P4) pellets, extruder, and conductive wire as in Example 12, the conductive wire was coated. The coating conditions were a cylinder temperature of 325 ° C., an extrusion rate of 8.8 g / min, a take-off speed of 15 m / min, an area withdrawal rate (R1) of 59, a parison length of 40 mm, and a pressure reduction of air between the conductor and the coating film of −1 cmHg. . The size of the coating die is 4mmφ for the outer diameter of the tip of the mandrel and 7 for the inner diameter of the die.
mmφ was used. Conductor is soft copper wire 0.4mmφ for electric wire
(JIS C3101) was used. The outer diameter of the obtained coated body was 0.86 mmφ, and a coated body having no irregularities on the surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 58 MPa, and the strength (B) at a strain of 10% was 48 MPa (B / A =
0.83), maximum strength is 86 MPa, elongation at break is 320
%Met. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 4 ° C. below (ΔTc ₁ = −4 ° C.).
The coated body was subjected to a heat aging test in an air circulation oven at 180 ° C. for 96 hours, and then a tensile test. As a result, the maximum strength was 76 MPa, and the elongation at break was 6%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%. This coating had an area withdrawing rate (R1) of 59 and a ΔTc ₁ of −4 ° C., all of which were small, and the molecular chain orientation of the coating film was insufficient. As a result, the elongation after the heat aging test ( (Elongation at break) was extremely small, and was inferior in bending resistance and flexibility.

Comparative Example 5 Polymer Synthesis Example 5 (Polymer P5 ) 390 kg of hydrous sodium sulfide (purity 46.40%) and NM
800 kg of P was charged into a titanium-clad polymerization vessel, and the temperature was gradually increased to about 200 ° C. in a nitrogen gas atmosphere.
147 kg of water were distilled off along with the molar hydrogen sulfide. Next, a mixed solution of 337.5 kg of p-DCB and 219 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 4.5 hours. Next, 80.8 kg of water was injected and 255 ° C.
After reacting for an hour, the temperature was lowered to 245 ° C., and the polymerization was continued for 11 hours. After cooling, the reaction mixture was
(100 mesh), the granular polymer was separated, washed with acetone and washed with water four times, and dehydrated to obtain a dried polymer.

[0064] supplying pelletized above-obtained polymer (P5) 44mmφ twin-screw kneading extruder to (Japan Steel Works TEX-44), and the mixture was kneaded at a cylinder temperature of 300 ° C. to 330 ° C., to obtain a pellet did. 310 ° C., shear rate 4 of the obtained polymer
The extensional viscosity at 00 / sec was 8,990 Pa · s. The melt viscosity η ^* measured at 310 ° C. and a shear rate of 1200 / sec was 390 Pa · s.

Wire Plating Experiment The pellets obtained above were supplied to a tabletop twin-screw extruder (MP-2015 manufactured by Tuba Co., APV) equipped with a wire coating die to cover the conductor. The coating conditions were a cylinder temperature of 325 ° C., an extrusion rate of 8.8 g / min, and a take-up speed of 40 m / min.
Min, area deduction rate (R1) 156, parison length 45
mm, and the pressure was reduced by 1 cmHg to remove air from the conductive wire and the coating film. The conductor is a soft copper wire for wire 0.4mmφ (JIS
C3101) was used. As the size of the coating die, a mandrel tip outer diameter of 4 mmφ and a die inner diameter of 7 mmφ were used. The outer diameter of the obtained coated body was 0.61 mmφ, and a coated body having no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 5
At 3 MPa, the strength (B) at a strain of 10% was 42 MPa (B / A = 0.79), the maximum strength was 90 MPa, and the elongation at break was 300%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 3 ° C. below (ΔTc
₁ = -3 ° C). The coating is placed in an air circulating oven for 180
After performing a heat aging test at 96 ° C. for 96 hours, a tensile test was performed. As a result, the maximum strength was 86 MPa, and the elongation at break was 6%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%. This coating had a small elongational viscosity and ΔTc ₁ of the resin. As a result, the elongation (elongation at break) after the heat aging test was extremely small, and the coating was inferior in bending resistance and flexibility.

Comparative Example 6 Polymer Synthesis Example 6 (Polymer P6 ) 420 kg of hydrous sodium sulfide (purity 46.21%) and NM
720 kg of P was charged into a titanium-clad polymerization vessel, and the temperature was gradually increased to about 200 ° C. in a nitrogen gas atmosphere, while the temperature was 61.8.
160 kg of water were distilled off together with the molar hydrogen sulphide. Next, a mixed solution of 363.6 kg of p-DCB and 250 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 4.5 hours. Next, 56.5 kg of water was injected and 255 ° C.
A time reaction was performed. After cooling, the reaction mixture is
The mixture was sieved with a screen of 100 μm (μm) to separate the granular polymer, washed with acetone three times, washed twice with water, 0.6%
After washing once with ammonium chloride, washing twice with water and washing with 0.06% ammonium chloride, the polymer was dehydrated and dried to obtain a polymer.

[0067] supplying pelletized above-obtained polymer (P6) 44mmφ twin-screw kneading extruder to (Japan Steel Works TEX-44), and the mixture was kneaded at a cylinder temperature of 300 ° C. to 320 ° C., prepared Perretto did. The elongational viscosity of the obtained polymer at 310 ° C. and a shear rate of 400 / sec was 4,000 Pa · s. The melt viscosity η ^* measured at 310 ° C. and a shear rate of 1200 / sec was 150 Pa · s.

Wire Plating Experiment The pellets obtained above were supplied to a desktop twin-screw extruder (MP-2015, manufactured by Tubaco APV) equipped with a wire coating die, and covered with a conductive wire. The coating conditions were as follows: cylinder temperature 310 ° C., extrusion rate 8.8 g / min, take-off speed 40 m /
Min, area deduction rate (R1) 156, parison length 15
mm, and the pressure of air bleeding between the conducting wire and the coating film was -5 cmHg. The conductor is soft copper wire for wire 0.4mmφ (JISC
3101) was used. As the size of the coating die, a mandrel tip outer diameter of 4 mmφ and a die inner diameter of 7 mmφ were used. During the coating of the conductive wire, resin breakage occurred at a frequency of twice per hour. The outer diameter of the obtained coated body was 0.61 mmφ, and a coated body having no uneven surface was obtained. A lead wire was pulled out from the coated body, and a tensile test of the coated film was performed. As a result, the yield strength (A) was 54 MPa, and the strength at a strain of 10% (B) was 43 MPa.
(B / A = 0.80), the maximum strength is 72 MPa,
The elongation at break was 300%. The conductor was removed from the coated body, and the difference between the temperature-induced crystallization temperatures of the coated film and the non-oriented press sheet was determined. 2 ° C. below (ΔTc
₁ = -2 ° C). The coating is placed in an air circulating oven for 180
After performing a heat aging test at 96 ° C. for 96 hours, a tensile test was performed. As a result, the maximum strength was 78 MPa, and the elongation at break was 4%. The crystallinity of the coating resin after the heat aging test was measured and was found to be 34%. This coating had a small elongational viscosity and ΔTc ₁ of the resin. As a result, the elongation (elongation at break) after the heat aging test was extremely small, and the coating was inferior in bending resistance and flexibility. Tables 2 to 4 show the results of these experiments.
Are shown together.

[0069]

[Table 2]

[0070]

[Table 3] (* 1) ETFE = ethylene-tetrafluoroethyne copolymer (* 2) PETS = pentaerythritol tristearate EMPS = epoxy-modified polysiloxane γAPES = γ-aminopropyltriethoxysilane

[0071]

[Table 4] (* 2) PETS = pentaerythritol tristearate

[0072]

According to the present invention, a PAS resin-coated metal member excellent in heat resistance, freon resistance, flame resistance, chemical resistance, radiation resistance, low-temperature physical properties, electrical insulation, mechanical properties, and the like is provided. Provided. The coated metal member of the present invention can be stably and continuously coated without causing resin breakage, and is excellent in tensile strength, flexibility, bending resistance and the like even when heat-treated after coating.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshikatsu Satake 16 Nishimachi Ochiai, Iwaki City, Fukushima Prefecture Kureha Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A coated metal member comprising a metal substrate coated with a polyarylene sulfide resin, wherein the polyarylene sulfide resin has an extensional viscosity of 10,000 Pa · s or more at 310 ° C. and a shear rate of 400 / sec. And the temperature-rise crystallization temperature of the polyarylene sulfide resin coating layer measured by a differential scanning calorimeter is 6 ° C. or more lower than the temperature-rise crystallization temperature of the non-oriented amorphous sheet of the polyarylene sulfide resin. Coated metal member. 2. The coated metal member according to claim 1, wherein the strength of the polyarylene sulfide resin coating layer at a strain of 10% is 0.93 times or more of the yield strength. 3. The coated metal member according to claim 1, wherein the crystallinity of the polyarylene sulfide resin coating layer after the heat treatment at a heat treatment temperature of 120 to 290 ° C. is in the range of 10 to 40%. 4. The coated metal member according to claim 3, wherein the strength of the polyarylene sulfide resin coating layer after heat treatment at a strain of 10% is 0.95 times or more of the yield strength. 5. The coated metal member according to claim 3, wherein the polyarylene sulfide resin layer after heat treatment has a breaking elongation of 30% or more. 6. The polyarylene sulfide resin according to claim 1, wherein the polyarylene sulfide resin is a branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihalo aromatic compound in the presence of a trihalo aromatic compound. 1
Item 7. The coated metal member according to item 1.