WO2022137781A1 - 樹脂組成物および電力ケーブル - Google Patents

樹脂組成物および電力ケーブル Download PDF

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Publication number
WO2022137781A1
WO2022137781A1 PCT/JP2021/039407 JP2021039407W WO2022137781A1 WO 2022137781 A1 WO2022137781 A1 WO 2022137781A1 JP 2021039407 W JP2021039407 W JP 2021039407W WO 2022137781 A1 WO2022137781 A1 WO 2022137781A1
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WO
WIPO (PCT)
Prior art keywords
resin
resistance
imparting agent
resin composition
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/039407
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
智 山▲崎▼
文俊 伊與田
孝則 山崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP2022571912A priority Critical patent/JP7666526B2/ja
Priority to US18/034,822 priority patent/US20230407070A1/en
Priority to CN202180071423.0A priority patent/CN116390979B/zh
Priority to DE112021006580.7T priority patent/DE112021006580T5/de
Publication of WO2022137781A1 publication Critical patent/WO2022137781A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • An insulating layer coated on the outer circumference of the conductor and Equipped with The insulating layer is formed of a resin composition and is formed from a resin composition.
  • the resin composition is Contains a resin component containing a propylene unit and a resistance-imparting agent,
  • the resistance-imparting agent is a monoma having a phenol skeleton and having hydrogen or an alkyl group having 1 to 3 carbon atoms bonded to at least one of the ortho positions of the hydroxyl groups in the phenol skeleton, and has a melting point of 215 ° C. or lower.
  • the molecular weight is 200 or more and 500 or less
  • the content of the resistance-imparting agent is 0.4 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component.
  • the content ratio of metal impurities is 0.02% or less by volume. Power cables are provided.
  • This additive is used as an antioxidant and has a phenol skeleton, and is composed of hydrogen or an alkyl group having 1 to 3 carbon atoms bonded to at least one of the ortho positions of the hydroxyl group in the phenol skeleton. It is a monoma having a molecular weight of 200 or more and 500 or less and a melting point of 215 ° C. or less, which is lower than the heating and mixing temperature of a propylene-based resin.
  • Metal impurities are, for example, mixed in at the material polymerization stage and the material mixing / extrusion stage, and are metal powders containing copper, iron, alloys thereof, or other metals used at the manufacturing site.
  • the size of the metal powder is not particularly limited, but is, for example, 50 ⁇ m or more and 500 ⁇ m or less.
  • the content of metal impurities, that is, the mixing amount is 0.02% or less in terms of volume ratio.
  • the content of metal impurities can be obtained, for example, by collecting a sample piece of 100 mm 3 from the resin composition, regarding the metal impurities contained in the sample piece as spherical, calculating the volume, and obtaining the volume ratio.
  • the ethylene content indicates the mass ratio of ethylene units to the ethylene units constituting the EPR and the propylene units.
  • the styrene resin does not have a melting point and a calorific value for melting.
  • the styrene resin a resin having no double bond in the chemical structure excluding the benzene ring is preferable.
  • the resin component may be thermally deteriorated at the time of molding the resin composition, and the characteristics of the obtained molded product may be deteriorated.
  • the resistance to heat deterioration is high, so that the characteristics of the molded product can be maintained higher.
  • the resin component containing the resistance-imparting agent and the propylene-based resin is mixed while heating at, for example, 200 ° C. to 220 ° C. because the melting point of the propylene-based resin is about 140 ° C. to 160 ° C. Therefore, the resistance-imparting agent having a melting point of 215 ° C. or lower tends to melt and become a liquid state during heating and mixing. Since this resistance-imparting agent has a polarity due to the phenolic skeleton and has a high affinity with metal impurities, when it is heated and mixed with the resin component, it collects around the metal impurities mixed in the resin component and collects the metal impurities. It is presumed to cover.
  • a monoma so-called hindered phenol antioxidant
  • a bulky substituent t-butyl group or the like
  • the steric hindrance is small and the reactivity of the hydroxyl group is high. It can be covered more reliably.
  • the content of the resistance-imparting agent is 0.4 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component. It is preferably 0.5 parts by mass or more and 8 parts by mass or less.
  • the resin composition may contain other additives, if necessary.
  • Other additives may include antioxidants, copper damage inhibitors, lubricants and colorants other than the above-mentioned resistance-imparting agents.
  • the resin composition is preferably non-crosslinked without cross-linking, but may contain a cross-linking agent for cross-linking.
  • a cross-linking agent for cross-linking it is preferable to carry out the cross-linking so that the gel fraction (degree of cross-linking) is low.
  • the residue is, for example, cumyl alcohol, ⁇ -methylstyrene, or the like.
  • the melting point and the amount of heat of melting of the resin composition vary depending on the contents of the propylene-based resin and the low crystallinity resin used as the resin component, and are indicators of the resin composition.
  • the melting point and heat of fusion of the resin composition are not particularly limited, but when random PP is contained as the propylene resin, the melting point is preferably 140 ° C. or higher and 150 ° C. or lower, and the heat of melting is preferably 55 J / g or higher and 100 J / g or lower. More preferably, the melting point is 140 ° C. or higher and 148 ° C.
  • the sheath 160 is provided so as to cover the outer periphery of the shielding layer 150.
  • the sheath 160 is made of, for example, polyvinyl chloride or polyethylene.
  • the insulating layer 130 of the present embodiment exhibits high insulating properties in the range where the content ratio of metal impurities is 0.02% or less in terms of volume ratio.
  • a 0.4 mm-thick sheet formed from the above-mentioned resin composition, in which a copper piece having a diameter of 200 ⁇ m or less is embedded as a metal impurity is used at room temperature at a commercial frequency (for example, 60 Hz).
  • a commercial frequency for example, 60 Hz.
  • Is applied at 10 kV for 10 minutes then boosted every 1 kV and applied for 10 minutes repeatedly, and the AC breakdown electric field strength is 45 kV / mm or more. That is, when the content ratio of the metal impurities is in the range of 0.02% or less in terms of volume ratio, the desired AC breaking electric field strength can be obtained in the insulating layer, and high insulating properties can be ensured.
  • the amount of each resin added is propylene-based, for example, when the total content of the propylene-based resin and the soft component containing at least one of the low crystalline resin and the styrene-based resin is 100 parts by mass.
  • the resin may be 55 parts by mass or more and 95 parts by mass or less, and the soft component may be 5 parts by mass or more and 45 parts by mass or less.
  • the content of the resistance-imparting agent shall be 0.4 parts by mass or more and 10 parts by mass or less when the total content of the propylene resin and the low crystalline resin is 100 parts by mass.
  • the shielding layer 150 is formed on the outside of the outer semi-conductive layer 140, for example, by winding a copper tape.
  • the resistance-imparting agent having a predetermined melting point and chemical structure, it can be melted when heated and mixed with the resin component to coat the surface of the metal impurities mixed in the resin component. That is, the resistance-imparting agent can be interposed at the interface between the metal impurity and the resin component. Since the resistance-imparting agent has an aromatic ring and polarity derived from the phenol skeleton, it alleviates the sudden change in resistance between the resin component and the metal impurities, and also alleviates the electric field concentration on the metal impurities, thereby making the metal. It is possible to suppress the deterioration of the insulating property due to impurities.
  • the melting point of the resistance-imparting agent is preferably 130 ° C. or lower, and more preferably the melting point of the resistance-imparting agent so that it becomes a liquid state at 27 ° C. According to the resistance-imparting agent having such a melting point, the surface of the metal impurity can be more reliably covered when the resin composition is heated and mixed, and the insulating property of the insulating layer can be further improved.
  • an evaluation sample imitating the insulating layer of a power cable was prepared by the following procedure.
  • a metal powder was added to the resin composition as a metal impurity to prepare an evaluation sample.
  • propylene-based resin (A).
  • Isotactic propylene homopolymer (homo PP): melt flow rate: 0.5 g / 10 min, density: 0.9 g / ml, melting point: 165 ° C., heat of fusion: 115 J / g
  • Random polypropylene (random PP): melt flow rate: 1.3 g / 10 min, density: 0.9 g / ml, melting point: 145 ° C., heat of fusion: 100 J / g
  • a copper material was scraped with a metal file to obtain a copper powder, which was separated by a sieve having an opening of 200 ⁇ m.
  • a resin composition was prepared in the same manner as in Sample 1 except that the resistance-imparting agent (D) was not added.
  • Samples 3 to 6 a resin composition was prepared in the same manner as in Sample 1, except that the amount of the component (d1) added was changed to 0.3 parts by mass, 0.5 parts by mass, 9 parts by mass, and 12 parts by mass, respectively. did.
  • Samples 16-18 In Samples 16 and 17, as shown in Table 5, the type of the propylene-based resin (A) was changed from homo-PP to random polypropylene (random PP), and the amount of each component added was changed. A resin composition was prepared in the same manner. In Sample 18, a resin composition was prepared in the same manner as in Samples 16 and 17, except that the resistance-imparting agent (D) was not added.
  • the comparative component (D) having a molecular weight outside the range of 200 to 500, having no phenol skeleton, causing steric hindrance around the hydroxyl group, or having a melting point higher than 215 ° C. Since ⁇ ) was used, it was confirmed that the insulating property was significantly lowered. This is because the comparative component (D') cannot sufficiently cover the surface of the metal impurity during heating and mixing, or even if it is covered, the resistance change between the metal impurity and the resin component cannot be sufficiently mitigated. it is conceivable that.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/039407 2020-12-21 2021-10-26 樹脂組成物および電力ケーブル Ceased WO2022137781A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022571912A JP7666526B2 (ja) 2020-12-21 2021-10-26 電力ケーブル
US18/034,822 US20230407070A1 (en) 2020-12-21 2021-10-26 Resin composition and power cable
CN202180071423.0A CN116390979B (zh) 2020-12-21 2021-10-26 树脂组合物以及电力电缆
DE112021006580.7T DE112021006580T5 (de) 2020-12-21 2021-10-26 Harzzusammensetzung und Stromkabel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020211491 2020-12-21
JP2020-211491 2020-12-21

Publications (1)

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WO2022137781A1 true WO2022137781A1 (ja) 2022-06-30

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PCT/JP2021/039407 Ceased WO2022137781A1 (ja) 2020-12-21 2021-10-26 樹脂組成物および電力ケーブル

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US (1) US20230407070A1 (https=)
JP (1) JP7666526B2 (https=)
CN (1) CN116390979B (https=)
DE (1) DE112021006580T5 (https=)
WO (1) WO2022137781A1 (https=)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012119196A (ja) * 2010-12-01 2012-06-21 Fujikura Ltd 伝送ケーブル用絶縁電線及び伝送ケーブル
JP2015162929A (ja) * 2014-02-26 2015-09-07 株式会社オートネットワーク技術研究所 電線保護材用組成物、電線保護材及びワイヤーハーネス
JP2017128677A (ja) * 2016-01-21 2017-07-27 株式会社Adeka 帯電防止性熱可塑性樹脂組成物およびそれを成形してなる成形体

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NL272489A (https=) * 1960-12-20 1964-08-25
JPS5769611A (en) 1980-10-16 1982-04-28 Showa Electric Wire & Cable Co Insulating compositon for power cable
WO1995009426A1 (en) * 1993-09-29 1995-04-06 University Of Connecticut An improved insulated electric cable
KR20170139696A (ko) * 2010-11-25 2017-12-19 프리즈미안 에스피에이 전압 안정화 열가소성 전기 절연층을 가진 에너지 케이블
US20180025957A1 (en) * 2015-02-25 2018-01-25 Toray Industries, Inc. Polyphenylene sulfide resin composition, molded product formed therefrom and method of producing semiconductor package
FR3045634B1 (fr) * 2015-12-18 2020-01-31 Nexans Composition polymere comprenant un liquide dielectrique presentant une polarite amelioree
TWI860420B (zh) 2019-11-18 2024-11-01 美商陶氏全球科技有限責任公司 抗熱老化之可撓性聚烯烴調配物
DE112021006581T5 (de) * 2020-12-21 2023-10-12 Sumitomo Electric Industries, Ltd. Harzzusammensetzung und Stromkabel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012119196A (ja) * 2010-12-01 2012-06-21 Fujikura Ltd 伝送ケーブル用絶縁電線及び伝送ケーブル
JP2015162929A (ja) * 2014-02-26 2015-09-07 株式会社オートネットワーク技術研究所 電線保護材用組成物、電線保護材及びワイヤーハーネス
JP2017128677A (ja) * 2016-01-21 2017-07-27 株式会社Adeka 帯電防止性熱可塑性樹脂組成物およびそれを成形してなる成形体

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* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Additives for plastics Adekas Tab Product List", ADDITIVES FOR PLASTICS ADEKA STAB PRODUCT LIST, JP, pages 1 - 4, XP009538019, Retrieved from the Internet <URL:https://web.archive.org/web/20210228183359/https://www.adeka.co.jp/chemical/products/plastic/pro111c.html> *
ANONYMOUS: "Nocrak 300", PRODUCT GUIDE. RUBBER CHEMICALS, ANTIOXIDANTS AND BISPHENOLS, 30 August 2022 (2022-08-30), JP, pages 1, XP009538640 *

Also Published As

Publication number Publication date
DE112021006580T5 (de) 2023-10-05
JP7666526B2 (ja) 2025-04-22
CN116390979A (zh) 2023-07-04
CN116390979B (zh) 2024-10-01
JPWO2022137781A1 (https=) 2022-06-30
US20230407070A1 (en) 2023-12-21

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