WO2010110273A1 - Tube thermorétrécissable en polyester - Google Patents

Tube thermorétrécissable en polyester Download PDF

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Publication number
WO2010110273A1
WO2010110273A1 PCT/JP2010/055000 JP2010055000W WO2010110273A1 WO 2010110273 A1 WO2010110273 A1 WO 2010110273A1 JP 2010055000 W JP2010055000 W JP 2010055000W WO 2010110273 A1 WO2010110273 A1 WO 2010110273A1
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WO
WIPO (PCT)
Prior art keywords
heat
component
tube
polyester
acid
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PCT/JP2010/055000
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English (en)
Japanese (ja)
Inventor
北島阿沙美
池田啓太
谷口浩一郎
Original Assignee
三菱樹脂株式会社
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Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to KR1020117024748A priority Critical patent/KR101373364B1/ko
Priority to CN201080004400.XA priority patent/CN102282198B/zh
Publication of WO2010110273A1 publication Critical patent/WO2010110273A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings

Definitions

  • the present invention relates to a polyester-based heat-shrinkable tube, and more particularly to a polyester-based heat-shrinkable tube that is particularly excellent in practical heat resistance and is suitable for coating electronic components, particularly capacitors such as aluminum electrolytic capacitors. .
  • a heat-shrinkable tube mainly made of polyvinyl chloride resin has been used as an electrical insulating material for coating electronic parts such as capacitors and batteries.
  • electronic parts such as capacitors and batteries.
  • High heat resistance has also been required for aluminum electrolytic capacitors used for substrates.
  • Polyvinyl chloride resin tubes are inexpensive but have insufficient heat resistance, and there are concerns about environmental problems associated with the generation of hydrogen chloride gas during combustion. As a result, heat-shrinkable tubes made of polyethylene terephthalate resin have been used.
  • the characteristics required for heat shrinkable tubes used for insulating materials for electronic parts such as capacitors are required to be properties such as coating finish, heat resistance, chemical resistance, and electrolyte resistance.
  • a heat shrink tube made of polyethylene terephthalate containing 9 to 15 mol% of neopentyl glycol as a diol component is used as a heat-shrinkable tube that is completely in close contact with the groove portion of the capacitor even in the dry heat treatment after the capacitor is coated and washed with water. Shrink tubing has been proposed.
  • the present invention has been made to solve the above-mentioned problems.
  • the problems of the present invention are particularly excellent in practical heat resistance, and are required for heat-shrinkable tubes such as electrical characteristics, chemical resistance, and electrolytic solution resistance.
  • An object of the present invention is to provide a polyester heat-shrinkable tube that satisfies the characteristics.
  • an object of the present invention is to provide a crystalline polyester (a) in which the main component of the acid component is terephthalic acid, the main component of the diol component is ethylene glycol, and the main component of the acid component is terephthalic acid.
  • Consists of a resin composition (A) whose main component is an amorphous polyester (b) containing a copolymer component other than ethylene glycol, and a differential thermal scanning calorimeter (DSC) according to JIS-K7121 This is achieved with a polyester heat-shrinkable tube (hereinafter also referred to as “tube of the present invention”) having a melting enthalpy ⁇ Hm value of 15 J / g to 35 J / g.
  • the content of the amorphous polyester (b) is preferably 1% by mass or more and 40% by mass or less with respect to 100% by mass of the resin composition (A).
  • the resin composition (A) further contains a crystalline polyester (c) in which the main component of the acid component is terephthalic acid and the main component of the diol component is 1,4-butanediol. Is preferred.
  • the amorphous polyester (b) preferably contains a diol component having an alicyclic structure as the diol component.
  • the diol component having an alicyclic structure is preferably 1,4-cyclohexanedimethanol.
  • the present invention it is possible to provide a polyester-based heat-shrinkable tube that is particularly excellent in practical heat resistance and satisfies the characteristics required for a heat-shrinkable tube such as electrical characteristics, chemical resistance, and electrolytic solution resistance. . Therefore, the present invention is useful as a coating material for electronic components including capacitors such as aluminum electrolytic capacitors.
  • the main component of the acid component is terephthalic acid
  • the main component of the diol component is ethylene glycol
  • the main component of the acid component is terephthalic acid.
  • the value of the melting enthalpy ⁇ Hm in the reheating process is 15 J / g or more and 35 J / g or less.
  • Resin composition (A) The resin composition (A) used in the tube of the present invention has a crystalline polyester (a) in which the main component of the acid component is terephthalic acid and the main component of the diol component is ethylene glycol, and the main component of the acid component is It is terephthalic acid, and the diol component contains amorphous polyester (b) containing a copolymer component other than ethylene glycol as a main component.
  • the crystalline polyester means that the temperature is raised from ⁇ 50 ° C. to 300 ° C. at a heating rate of 10 ° C./min using DSC according to JIS-K7121, and kept at 300 ° C. for 1 minute, and then ⁇ 50 ° C.
  • the temperature was lowered to 10 ° C. at a cooling rate of 10 ° C./min, held at ⁇ 50 ° C. for 1 minute, and then heated again to 300 ° C. at a heating rate of 10 ° C./min, a clear melting peak was observed at the second temperature rise. It refers to the polyester resin that appears.
  • the acid component is mainly composed of terephthalic acid
  • the diol component is mainly composed of ethylene glycol.
  • the main components terephthalic acid and ethylene glycol are contained in the acid component or diol component in a proportion of 51 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more.
  • the crystalline polyester (a) may contain other copolymerization components in the acid component or the diol component as long as they are in the range of 49 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less. .
  • Examples of other copolymerizable acid components include isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl Dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4 -Aromatic dicarboxylic acid components derived from diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3 -From cyclohexane
  • Examples of other copolymerizable diol components include diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and trans-tetramethyl- 1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, spiroglycol, p-xylenediol, bisphenol A And diol components derived from tetrabromobisphenol A, tetrabromobisphenol A-bis
  • These crystalline polyesters (a) may be used alone or in combination of two or more.
  • Examples of commercially available crystalline polyester (a) include “Novapex” series (manufactured by Mitsubishi Chemical Corporation), “Unipet” (manufactured by Nippon Unipet Corporation), and the like.
  • the non-crystalline polyester means that, according to JIS-K7121, the temperature is raised from ⁇ 50 ° C. to 300 ° C. at a heating rate of 10 ° C./min using DSC, and is kept at 300 ° C. for 1 minute, When the temperature was lowered to 50 ° C. at a cooling rate of 10 ° C./min, held at ⁇ 50 ° C. for 1 minute, and then heated again to 300 ° C. at a heating rate of 10 ° C./min, a clear melting peak was obtained at the second temperature rise. Refers to a polyester resin that does not appear.
  • the acid component of the amorphous polyester (b) is mainly composed of terephthalic acid
  • the diol component is mainly composed of ethylene glycol
  • the copolymer component other than ethylene glycol is 1 mol% or more, preferably 15 mol% or more, more preferably 25 mol. % Or more and 49 mol% or less, preferably 45 mol% or less.
  • diol components that can be copolymerized are the same as those shown for the crystalline polyester (a), but the diol components are diethylene glycol, trans-tetramethyl-1,3-cyclobutanediol, 2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3- It is preferably at least one selected from the group consisting of cyclohexanediol, spiroglycol, and polytetramethylene glycol.
  • the content of the diol component having an alicyclic structure is 1 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more in the total diol component of the amorphous polyester (b), and the upper limit is 49 mol. % Or less, preferably 45 mol% or less.
  • the temperature is increased from ⁇ 50 ° C. to 300 ° C. at a heating rate of 10 ° C./min using DSC in accordance with JIS-K7121, and 1 at 300 ° C. The temperature is lowered to ⁇ 50 ° C.
  • the glass transition temperature (Tg) of the amorphous polyester (b) is preferably 80 ° C. or higher and 120 ° C. or lower, and those having a higher Tg than the crystalline polyester (a) to be used are further included. preferable.
  • the glass transition temperature (Tg) of the amorphous polyester (b) is in the above range, the heat resistance derived from the high Tg and the content of the amorphous polyester (b) melt the resin composition (A). Since it is easy to control the enthalpy ⁇ Hm value, (1) a flux swell test, (2) a cleaning swell test, and (3) a high temperature storage test described later can be satisfied at the same time, which is preferable.
  • amorphous polyester for example, “Eastar Copolyester 6863”, “Easter Copolyester GN001” (manufactured by Eastman Chemical), “TRITAN” (manufactured by Eastman Chemical), “SKYGREEN PETG S2008” (Manufactured by SK Chemical Co., Ltd.), “ALTERSTER” (manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like.
  • the content of the amorphous polyester (b) contained in the resin composition (A) is 1% by mass or more, preferably 100% by mass or more, preferably 100% by mass of the crystalline polyester (a) and the amorphous polyester (b). It is 5 mass% or more, More preferably, it is 10 mass% or more, 40 mass% or less, Preferably it is 35 mass% or less, More preferably, it can be 30 mass% or less. If the content of the amorphous polyester (b) is within the above range, the resin composition (A) is provided with practically excellent heat resistance without impairing the characteristics of the crystalline polyester such as chemical resistance. Can do.
  • the tube of the present invention further comprises a crystalline polyester (c) in which the main component of the acid component is terephthalic acid and the main component of the diol component is 1,4-butanediol in the resin composition (A). Can do.
  • the crystalline polyester (c) in the resin composition (A) the glass transition temperature Tg and the crystallization speed of the resin composition (A) can be adjusted.
  • the content of the crystalline polyester (c) is 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass with respect to 100% by mass of the resin composition (A). The following is desirable.
  • Examples of commercially available crystalline polyester (c) include “Novaduran” (manufactured by Mitsubishi Chemical Engineering Plastics), “Duranex” (manufactured by Wintech Polymer), and the like.
  • the tube of the present invention is not limited to the resin composition (A) as long as the effects of the present invention are not hindered, such as thermoplastic elastomers such as polyester-based, olefin-based copolymers, and polystyrene-based resins. Resin). Furthermore, other components can be appropriately added to the resin composition (A) depending on the application.
  • an organic lubricant for example, an organic lubricant, an inorganic lubricant, an inorganic filler, or an impact resistance improver, a filler, an ultraviolet absorber, a surface treatment agent, a light stabilizer, a pigment, an antistatic agent for improving easy lubricity of the tube, Auxiliaries such as antibacterial agents, crosslinking agents, antioxidants, flame retardants, plasticizers, processing aids, foaming agents and the like can be blended.
  • the tube of the present invention has a melting enthalpy ⁇ Hm of 15 J / g or more, preferably 18 J / g or more, more preferably 20 J / g or more in the reheating process measured by DSC. , 35 J / g or less.
  • the tube of the present invention can exhibit heat resistance when the value of the melting enthalpy ⁇ Hm is in the above range, and thus can be suitably used as a coating material for capacitors and batteries.
  • the tube that is once in close contact with the coating such as a capacitor loosens due to crystal growth when exposed to a high temperature such as a capacitor mounting process. Dots tend to occur. If it is less than 15 J / g, the characteristics of the crystalline resin such as heat resistance and chemical resistance may be impaired.
  • a copolymer composition of the crystalline polyester (a) in the resin composition (A), an amorphous polyester (b), and others The method of adjusting the combination of these resin, a compounding ratio, and intrinsic viscosity is mentioned.
  • a method for adjusting the copolymer composition of the crystalline polyester (a) in the resin composition (A) or a method for adjusting the blending ratio of the resin composition (A) is preferably used.
  • the content of the crystalline polyester (a) is increased, the content of the amorphous polyester (b) is decreased, and the crystalline polyester (c ) And a means for reducing the types of monomers used for the acid component and the diol component in the copolymer composition of the crystalline polyester (a) in the resin composition (A).
  • the content of the crystalline polyester (a) is decreased and the content of the amorphous polyester (b) is increased or the crystal in the resin composition (A).
  • the copolymer composition of the reactive polyester (a) there are means such as increasing the types of monomers used for the acid component and the diol component.
  • the value of the melting enthalpy ⁇ Hm is usually in the range of 45 J / g or more and 60 J / g or less.
  • the value of ⁇ Hm can be reduced by adjusting the type and number of monomers used for the acid component and diol component of the copolymer composition.
  • the melting temperature Tm also decreases, and the heat resistance of the entire resin composition (A) decreases.
  • the content of the amorphous polyester (b) is also adjusted in combination.
  • the kind and content of the acid component and diol component which are copolymerization components can be qualitatively and quantitatively analyzed by a well-known method, for example, a nuclear magnetic resonance (NMR) measuring apparatus and other instrumental analyzers.
  • NMR nuclear magnetic resonance
  • the melting enthalpy ⁇ Hm was measured from -50 ° C. at a heating rate of 10 ° C./min according to JIS-K7121, using 10 mg of the sample cut from the heat-shrinkable tube formed using DSC-7 manufactured by Perkin Elmer.
  • the temperature was raised to 300 ° C., held at 300 ° C. for 1 minute, cooled to ⁇ 50 ° C. at a cooling rate of 10 ° C./minute, held at ⁇ 50 ° C. for 1 minute, and then again heated to 300 ° C. at a heating rate of 10 ° C./minute. It can be obtained from the thermogram when the temperature is raised to.
  • the tube manufacturing method of the present invention is a tube manufacturing method of the present invention, which can be formed by a normal tubular method, and after the above-described polyester raw material is melted, it is extruded into a cylindrical shape with an annular die and molded. Is achieved.
  • the unstretched tube is 1.2 times or more in the radial direction, preferably 1.3 times or more, more preferably 1.4 times or more and 3.0 times or less, preferably 2.5 times or less.
  • the draw ratio in the length direction of the tube is 2.0 times or less, the shrinkage amount in the length direction becomes too large, and the coating position shifts when the electronic parts are coated, or the cut length Since it is not necessary to lengthen the length, cost increase can be suppressed.
  • the thickness of the tube obtained as described above is not particularly limited, the thickness of the tube generally used for a capacitor is typically in a range from about 0.05 mm to 1.0 mm depending on the rated voltage of the capacitor. The one in the range from 0.07 mm to 0.2 mm is used. Further, a tube having a folded width (hereinafter referred to as “folded diameter”) in the range of 4 mm to 300 mm is preferable in that it can be applied to general-purpose capacitors and battery coatings and general-purpose battery packaging in general.
  • the tube of the present invention is composed of the above resin composition, and the one having a specific heat shrinkage is particularly excellent in performance as a coating material for capacitors and batteries, (1)
  • the shrinkage in the length direction when immersed in warm water at 100 ° C. for 10 seconds is 2% or more, preferably 3% or more, more preferably 5% or more, 20% or less, preferably 15% or less. More preferably, it is 12% or less.
  • the shrinkage in the radial direction is 15% or more, preferably 20% or more, more preferably 25% or more, and is 60% or less, preferably 50% or less, more preferably 45% or less. More preferably, those satisfying the following characteristics as in (1) are preferred.
  • the shrinkage in the length direction when immersed in warm water at 80 ° C. for 10 seconds is 2% or more, preferably 3% or more, more preferably 5% or more, and 15% or less, preferably 12% or less. More preferably, it is 10% or less.
  • the shrinkage in the radial direction is 10% or more, preferably 15% or more, more preferably 20% or more, and is 60% or less, preferably 50% or less, more preferably 45% or less.
  • the tube of the present invention has a melting enthalpy ⁇ Hm value within a predetermined range, the heat-shrinkable tube does not expand after completion of the capacitor manufacturing process and the board mounting process, and has heat resistance in practical use. In addition, it has excellent performance as a coating material for capacitors and batteries.
  • the cleaning swelling test is a test method for evaluating the expansion of the heat-shrinkable tube in the capacitor manufacturing process. Specifically, after coating with a nichrome wire heater at 300 ° C. for 3.6 seconds, it was immersed continuously in normal temperature water for 15 minutes, 60 ° C. warm water for 30 minutes, and further in normal temperature water for 15 minutes. After exposure in an oven at 95 ° C.
  • the cause of the expansion of the heat-shrinkable tube after the cleaning swell test is that water enters the gap between the coated tube and the capacitor when immersed in water at normal temperature and 60 ° C hot water twice. When exposed to a medium 95 ° C atmosphere, the water entering the gap evaporates and the volume increases, so the pressure in the gap between the coated tube and the capacitor rises, and the coated tube is expected to expand. .
  • the flux swell test is a test method for evaluating the expansion of the tube during board mounting. Specifically, it is coated with a 300 ° C.
  • nichrome wire heater for 3.6 seconds, heat-treated in a hot air circulation oven in an atmosphere at 85 ° C. for 60 minutes, and then a flux (for example, Hiroki Co., Ltd.) is formed on the sealing portion of the capacitor.
  • JS-E-11 was applied, and the substrate mounted so that the substrate and the capacitor sealing part were in close contact with each other was again exposed to 160 ° C in a hot air circulation oven for 2 minutes.
  • Evaluate by The cause of the expansion of the tube after the flux expansion test is that the flux applied to the sealing portion of the capacitor penetrates into the gap between the coated tube and the capacitor and is then exposed to a 160 ° C. atmosphere in a hot air circulation oven.
  • the high-temperature standing test is a test method for evaluating heat resistance, which is covered with a nichrome wire heater at 300 ° C. for 3.6 seconds and subjected to aging in a hot air circulation oven for 60 minutes in an 85 ° C. atmosphere. After that, the appearance of the coated tube after being exposed to a 150 ° C. atmosphere for 60 minutes in a hot air circulation oven again is visually evaluated.
  • the cause of the expansion of the tube after the high-temperature standing test is that the heat-shrinkable tube made of a conventional polyethylene terephthalate resin crystallizes when exposed to a 150 ° C. atmosphere in a hot-air circulating oven, and the crystal itself It is presumed that the volume of the tube increases due to the expansion and interference between the crystals, and the expansion of the coated tube occurs.
  • a heat-shrinkable tube that does not clear any of the above (1) flux swell test, (2) cleaning swell test, and (3) high-temperature standing test does not cause the tube to expand after the capacitor manufacturing process or the board mounting process is completed. As a result, mounting processing cannot be performed, and heat resistance in actual use deteriorates. On the contrary, if it is a heat shrinkable tube that clears all the tests of (1), (2), and (3) above, it can be mounted without impairing the appearance of the coated tube after the capacitor manufacturing process or board mounting process. Can be processed.
  • the tube of the present invention contains a copolymer composition of crystalline polyester (a), amorphous polyester (b), and other resins.
  • the value of the melting enthalpy ⁇ Hm in the re-heating process measured by a differential thermal scanning calorimeter (DSC) according to JIS-K7121 is adjusted from 15 J / g to 35 J / g, preferably 20 J. / G to 35 J / g.
  • the member covered with the tube of the present invention can be suitably used for covering a capacitor such as an aluminum electrolytic capacitor, but other uses such as electric wires (round wire, square wire), dry batteries, It can also be used as a secondary battery such as a lithium ion battery, an electric device such as a steel tube or a motor coil end, a transformer, a small motor, or a fluorescent lamp covering tube of a light bulb, a fluorescent lamp, a facsimile or an image scanner.
  • main component in the present invention includes the intention that a component other than the main component may be contained.
  • content ratio with respect to all components is not particularly limited, it is necessary to occupy at least 50% (mol% or mass%) of all components (when the main component is 2 components or more, the total value is 50% or more) In particular, it is preferably 60% or more, particularly preferably 70% or more, and more preferably 90% or more (including 100%).
  • a tube having a folding diameter of 16.8 mm, a wall thickness of 0.08 mm, and a length of 16.1 mm is placed on an aluminum electrolytic capacitor having a diameter of 10 mm and a length of 12.5 mm for 3.6 seconds with a 300 ° C. nichrome wire heater. After being coated, the film was immersed in normal temperature water for 15 minutes, 60 ° C. warm water for 30 minutes, and further normal temperature water for 15 minutes. Then, it exposed to 95 degreeC atmosphere in a hot-air circulation type oven for 60 minutes, and the external appearance of the capacitor
  • Solvent resistance test A tube having a folding diameter of 16.8 mm, a wall thickness of 0.08 mm, and a length of 16.1 mm is mounted on an aluminum electrolytic capacitor having a diameter of 10 mm and a length of 12.5 mm with a 300 ° C. nichrome wire heater. Then, heat treatment was performed in an oven at 85 ° C. for 60 minutes in a hot air circulating oven. After immersing in each test solvent for a predetermined time, the appearance of the capacitor-coated tube dried at room temperature for 1 hour was visually evaluated as follows. Test solvent 1: Acetone Immersion time: 30 seconds Test solvent 2: Xylene Immersion time: 5 minutes ( ⁇ ) Good appearance without swelling and cracking in the tube. (X) Swelling, cracking, etc. occur remarkably in the tube and it cannot be used due to poor appearance.
  • PET5 Unipet
  • Inorganic lubricant 1 Silica having an average particle size of 4.0 ⁇ m
  • Hydrolysis inhibitor 1 Starbazole 100 (manufactured by Rhein Chemie; high molecular weight polycarbodiimide compound)
  • Examples 1 to 5 and Comparative Examples 1 to 4 The resin composition prepared with the composition described in Table 1 is dissolved in an extruder set at a cylinder temperature of 280 ° C., extruded through a round die, immersed in water, and cooled and solidified to obtain an original tube before stretching.
  • the original tube was subsequently heated with hot water at 90 ° C., stretched 1.05 to 1.1 times in the length direction and 1.7 to 1.8 times in the radial direction, and then cooled to a folding diameter of 8.6 mm.
  • a polyester heat-shrinkable tube having a thickness of 70 ⁇ m, a folding diameter of 16.8 mm, and a thickness of 80 ⁇ m was obtained.
  • Table 1 shows the results of evaluating the characteristics of the tube obtained by tubular molding.
  • the tubes of the present invention are free of blistering and loosening even at high temperatures, have a good coating appearance, and have good flux swell test and washing swell test. Also in the solvent property test, the tube had good appearance without swelling or cracking.
  • tubes (Comparative Examples 1 to 4) in which the value of the melting enthalpy ⁇ Hm in the re-heating process measured by the differential thermal scanning calorimeter (DSC) is outside the specified range of the present invention (Comparative Examples 1 to 4) It can be confirmed that any one or more of the cleaning blister test, the high temperature storage test and the solvent resistance test is inferior.
  • the tube of the present invention is a polyester heat-shrinkable tube that is particularly excellent in practical heat resistance and satisfies the characteristics required for heat-shrinkable tubes such as electrical properties, chemical resistance, and electrolytic solution resistance. I understand.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention propose un tube thermorétrécissable dont la résistance thermique est, dans la pratique, particulièrement élevé et qui possède les caractéristiques particulières requises pour les tubes thermorétrécissables en termes de propriétés électriques, de résistance chimique,et de résistance aux solutions électrolytiques. Le tube est formé d'une composition de résine (A) qui comprend en tant que composants principaux d'une part un polyester cristallin (a) dans lequel l'acide téréphtalique est le composant principal du composé acide, et dans lequel l'éthylène glycol est le composant principal du composé diol, et d'autre part, un polyester non cristallin (b) dans lequel l'acide téréphtalique est le composant principal du composé acide, et qui comprend un copolymère dont le composé diol est autre que l'éthylène glycol. Mesurée par calorimétrie différentielle à balayage (DSC), conformément à la norme JIS-K7121, selon le processus répété d'élévation de température, la valeur de l'enthalpie de fusion ΔHm est égale ou supérieure à 15J/g et égale ou inférieure à 35 J/g.
PCT/JP2010/055000 2009-03-23 2010-03-23 Tube thermorétrécissable en polyester WO2010110273A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020117024748A KR101373364B1 (ko) 2009-03-23 2010-03-23 폴리에스터계 열수축성 튜브
CN201080004400.XA CN102282198B (zh) 2009-03-23 2010-03-23 聚酯类热收缩管

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WO2015077409A1 (fr) * 2013-11-25 2015-05-28 Tyco Electronics Corporation Tube thermiquement rétrécissable et système comprenant une tubulure thermiquement rétrécissable thermiquement récupérée
WO2015077739A1 (fr) * 2013-11-25 2015-05-28 Tyco Electronics Corporation Tube thermorétractable
JP2016200792A (ja) * 2015-04-13 2016-12-01 三菱樹脂株式会社 反射フィルム、及びこれを備えてなる液晶表示装置、照明装置、装飾用物品
JP2017008122A (ja) * 2015-06-16 2017-01-12 ユニチカ株式会社 ポリエステル樹脂組成物およびそれを用いて得られる成形体
WO2020218324A1 (fr) * 2019-04-25 2020-10-29 三菱瓦斯化学株式会社 Composition de résine polyester, article moulé par injection de polyester, article moulé par extrusion de polyester, mousse de polyester, récipient en polyester, bouteille en polyester, vaisselle en polyester et biberon en polyester
EP3778726A4 (fr) * 2018-03-27 2022-01-05 Dai Nippon Printing Co., Ltd. Film de poly(téréphtalate d'éthylène) pour matériau d'emballage de cellule, matériau d'emballage de cellule, procédé pour la fabrication de matériau d'emballage de cellule et cellule

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JP6645754B2 (ja) * 2015-06-16 2020-02-14 ユニチカ株式会社 ポリエステル樹脂組成物およびそれを用いて得られる成形体
CN109401217B (zh) * 2017-08-16 2022-06-21 中国石油化工股份有限公司 聚酯组合物和热收缩套管及其制备方法
CN109694467A (zh) * 2017-10-24 2019-04-30 中国石油化工集团公司 Pbt耐热改性方法
CN109694470A (zh) * 2017-10-24 2019-04-30 中国石化仪征化纤有限责任公司 一种高耐热无定形聚酯的制备方法
WO2021148258A1 (fr) * 2020-01-21 2021-07-29 Basf Se Composition à base de pbt
KR20240004952A (ko) * 2021-08-31 2024-01-11 다키론 씨아이 가부시키가이샤 폴리에스테르계 열 수축 필름

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN103370372A (zh) * 2011-02-18 2013-10-23 绿安全股份有限公司 在自然环境条件下和比其严酷的自然环境条件下或者与其同样或在其以上的严酷的使用条件下稳定，耐化学性和耐久性优异的透明树脂组合物及使用其的制品
CN103370372B (zh) * 2011-02-18 2016-06-15 绿安全股份有限公司 在自然环境条件下和比其严酷的自然环境条件下或者与其同样或在其以上的严酷的使用条件下稳定，耐化学性和耐久性优异的透明树脂组合物及使用其的制品
EP2677001A4 (fr) * 2011-02-18 2016-10-19 Midori Anzen Co Ltd Composition de résine transparente à bonne résistance chimique, durabilité et stabilité dans des conditions ambiantes naturelles, dans des conditions ambiantes naturelles plus difficiles, et dans des conditions d'utilisation similaires ou plus difficiles, et produit utilisant cette composition
US9550885B2 (en) 2011-02-18 2017-01-24 Midori Anzen Co., Ltd. Transparent resin composition having good chemical resistance, durability and stability under natural environmental conditions, harsher natural environmental conditions, and similar or harsher usage conditions, and product using same
WO2015077409A1 (fr) * 2013-11-25 2015-05-28 Tyco Electronics Corporation Tube thermiquement rétrécissable et système comprenant une tubulure thermiquement rétrécissable thermiquement récupérée
WO2015077739A1 (fr) * 2013-11-25 2015-05-28 Tyco Electronics Corporation Tube thermorétractable
JP2016200792A (ja) * 2015-04-13 2016-12-01 三菱樹脂株式会社 反射フィルム、及びこれを備えてなる液晶表示装置、照明装置、装飾用物品
JP2017008122A (ja) * 2015-06-16 2017-01-12 ユニチカ株式会社 ポリエステル樹脂組成物およびそれを用いて得られる成形体
EP3778726A4 (fr) * 2018-03-27 2022-01-05 Dai Nippon Printing Co., Ltd. Film de poly(téréphtalate d'éthylène) pour matériau d'emballage de cellule, matériau d'emballage de cellule, procédé pour la fabrication de matériau d'emballage de cellule et cellule
WO2020218324A1 (fr) * 2019-04-25 2020-10-29 三菱瓦斯化学株式会社 Composition de résine polyester, article moulé par injection de polyester, article moulé par extrusion de polyester, mousse de polyester, récipient en polyester, bouteille en polyester, vaisselle en polyester et biberon en polyester
EP3960807A4 (fr) * 2019-04-25 2022-06-15 Mitsubishi Gas Chemical Company, Inc. Composition de résine polyester, article moulé par injection de polyester, article moulé par extrusion de polyester, mousse de polyester, récipient en polyester, bouteille en polyester, vaisselle en polyester et biberon en polyester

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CN102282198A (zh) 2011-12-14
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