WO2016208656A1 - 難燃性樹脂組成物、及び、これを用いたケーブル並びに光ファイバケーブル - Google Patents
難燃性樹脂組成物、及び、これを用いたケーブル並びに光ファイバケーブル Download PDFInfo
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- WO2016208656A1 WO2016208656A1 PCT/JP2016/068610 JP2016068610W WO2016208656A1 WO 2016208656 A1 WO2016208656 A1 WO 2016208656A1 JP 2016068610 W JP2016068610 W JP 2016068610W WO 2016208656 A1 WO2016208656 A1 WO 2016208656A1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 91
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- 150000001875 compounds Chemical class 0.000 claims abstract description 91
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 79
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 79
- -1 amine compound Chemical class 0.000 claims abstract description 63
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- 229930195729 fatty acid Natural products 0.000 claims abstract description 45
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 45
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 39
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
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- BEOUGZFCUMNGOU-UHFFFAOYSA-N tuberculostearic acid Chemical compound CCCCCCCCC(C)CCCCCCCCC(O)=O BEOUGZFCUMNGOU-UHFFFAOYSA-N 0.000 description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 2
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- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 0 *NCCCNCCN(*)CCCN* Chemical compound *NCCCNCCN(*)CCCN* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- 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
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- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C08K5/3492—Triazines
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- G—PHYSICS
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- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
Definitions
- the present invention relates to a flame retardant resin composition, a cable using the same, and an optical fiber cable.
- eco-materials are widely used for cable coverings, cable jackets, tubes, tapes, packaging materials, building materials, and the like.
- flame retardancy is obtained by adding calcium carbonate as a flame retardant to a polyolefin resin and adding a silicone compound such as silicone gum and a fatty acid-containing compound such as magnesium stearate as a flame retardant aid.
- Resin compositions are known (see Patent Document 1 below).
- the present invention has been made in view of the above circumstances, and has a flame-retardant resin composition capable of ensuring excellent mechanical properties and excellent flame retardancy, and a cable and an optical device using the same.
- An object is to provide a fiber cable.
- the present inventors have repeatedly studied to solve the above problems. As a result, the present inventors added the triazine ring-containing hindered amine compound containing an oxygen atom in a predetermined ratio to the polyolefin resin in addition to the calcium carbonate, the silicone compound, and the fatty acid-containing compound. I found out that it could be solved.
- the present invention includes a polyolefin-based resin, a silicone-based compound, a fatty acid-containing compound, calcium carbonate, and a triazine ring-containing hindered amine-based compound, and the silicone-based compound is based on 100 parts by mass of the polyolefin-based resin. 1.5 parts by mass or more and 10 parts by mass or less, and the fatty acid-containing compound is compounded at a ratio of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyolefin-based resin.
- the triazine ring-containing hindered amine compound is 0.05 parts by mass or more with respect to 100 parts by mass of the polyolefin resin.
- the triazine ring-containing hinder Doamin based compound is a flame retardant resin composition containing an oxygen atom.
- the flame-retardant resin composition of the present invention it is possible to ensure excellent mechanical properties and excellent flame retardancy.
- the present inventors infer the reason why the above effect is obtained in the flame retardant resin composition of the present invention as follows.
- the flame retardant resin composition contains a triazine ring-containing hindered amine compound having an oxygen atom, oxygen radicals are generated from the triazine ring-containing hindered amine compound during combustion of the flame retardant resin composition, By capturing the hydrogen radicals generated by the decomposition of the polyolefin resin during the combustion of oxygen radicals, the combustion of the polyolefin resin is suppressed.
- the triazine ring-containing hindered amine compound can effectively suppress the combustion of the polyolefin resin due to the radical scavenging effect even in a small amount. Therefore, it becomes possible to reduce the compounding quantity with respect to the polyolefin resin of a triazine ring containing hindered amine type compound, As a result, it is thought that the outstanding mechanical characteristic is ensured.
- the triazine ring-containing hindered amine compound is preferably blended at a ratio of 0.1 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- the triazine ring-containing hindered amine compound preferably has a group represented by the following formula (1).
- R 1 to R 4 are each independently an alkyl group having 1 to 8 carbon atoms
- R 5 is an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.
- R 1 to R 4 each independently represents an alkyl group having 1 to 3 carbon atoms, and R 5 represents a cycloalkyl group.
- the triazine ring-containing hindered amine compound is preferably represented by the following formula (2).
- R 6 to R 8 each independently represents a group represented by the following formula (3)
- R 9 and R 10 each independently represent a group represented by the above formula (1)
- R 11 and R 12 each independently represents an alkyl group having 1 to 18 carbon atoms.
- the triazine ring-containing hindered amine compound is a compound represented by the formula (2), and R 1 to R 4 in the formula (1) are each independently a carbon number.
- R 1 represents an alkyl group having 1 to 3;
- R 5 represents a cycloalkyl group having 5 to 8 carbon atoms;
- R 11 and R 12 in the formula (3) are composed of compounds having an alkyl group having 1 to 6 carbon atoms. It is preferable.
- the silicone compound is blended at a ratio of 1.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the polyolefin resin, and the fatty acid-containing compound is the polyolefin. 3 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the resin, and the calcium carbonate is compounded at a ratio of 10 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable.
- the polyolefin resin is at least one selected from the group consisting of polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and polypropylene. Preferably, it is configured.
- the present invention is also a cable comprising a conductor and at least one insulator covering the conductor, wherein the insulator is made of the above-mentioned flame retardant resin composition.
- the present invention is an optical fiber cable having an optical fiber and an insulator covering the optical fiber, wherein the insulator is composed of the above-mentioned flame retardant resin composition.
- a flame retardant resin composition capable of ensuring excellent mechanical properties and ensuring excellent flame retardancy, a cable using the same, and an optical fiber cable.
- FIG. 2 is a cross-sectional view taken along line II-II in FIG. It is sectional drawing which shows one Embodiment of the optical fiber cable of this invention.
- FIG. 1 is a partial side view showing an embodiment of a cable according to the present invention.
- FIG. 2 is a sectional view taken along line II-II in FIG.
- the round cable 10 includes an insulated wire 4 and a tube-shaped outer sheath 3 as an insulator that covers the insulated wire 4.
- the insulated wire 4 includes an inner conductor 1 as a conductor and a tubular insulator 2 that covers the inner conductor 1. That is, the round cable 10 is a metal cable.
- the internal conductor 1 is provided inside the tubular insulator 2 and is provided inside the tubular jacket 3.
- the tubular insulator 2 and the jacket 3 are made of a flame retardant resin composition
- the flame retardant resin composition includes a polyolefin resin, a silicone compound, a fatty acid-containing compound, It contains calcium carbonate and a triazine ring-containing hindered amine compound, the silicone compound is blended at a ratio of 1.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyolefin resin, and the fatty acid-containing compound is a polyolefin.
- the ring-containing hindered amine compound is 0.05 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. Is blended in an amount of full, triazine ring-containing hindered amine compound contains an oxygen atom.
- the insulator 2 and the jacket 3 made of the flame retardant resin composition can ensure excellent mechanical properties while ensuring excellent flame retardancy.
- the inner conductor 1 as a conductor is prepared.
- the inner conductor 1 may be composed of only one strand, or may be configured by bundling a plurality of strands. Further, the inner conductor 1 is not particularly limited with respect to the conductor diameter, the material of the conductor, and the like, and can be appropriately determined according to the application.
- a metal such as copper can be used as the internal conductor 1.
- the flame retardant resin composition is prepared.
- the flame retardant resin composition includes a polyolefin resin, a silicone compound, a fatty acid-containing compound, calcium carbonate, and a triazine ring-containing hindered amine compound.
- polyolefin resin examples include polyethylene (PE), acid-modified polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), polypropylene (PP), Examples thereof include ethylene-methyl acrylate copolymer (EMA), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, and olefin-based thermoplastic elastomer. These can be used alone or in combination of two or more.
- PE polyethylene
- EVA ethylene-vinyl acetate copolymer
- ESA ethylene-ethyl acrylate copolymer
- PP polypropylene
- EMA ethylene-methyl acrylate copolymer
- EMA ethylene-propylene copolymer
- ethylene-butene copolymer ethylene-butene copolymer
- the polyolefin resin is preferably composed of at least one selected from the group consisting of polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and polypropylene.
- the silicone compound functions as a flame retardant aid, and examples of the silicone compound include polyorganosiloxane.
- the polyorganosiloxane has a siloxane bond in the main chain and an organic group in the side chain.
- the organic group include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and aryl groups such as vinyl group, phenyl group, and naphthyl group.
- polyorganosiloxane examples include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, and methyl (3,3,3-trifluoropropyl) polysiloxane. Is mentioned.
- the polyorganosiloxane is used in the form of silicone oil, silicone powder, silicone gum or silicone resin. Among these, the polyorganosiloxane is preferably used in the form of silicone gum. In this case, bloom is less likely to occur.
- the silicone compound is blended at a ratio of 1.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.
- more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the silicone compound is less than 1.5 parts by mass.
- the compounding ratio of the silicone compound with respect to 100 parts by mass of the polyolefin resin is within the above range, the non-flammability unevenness is reduced as compared with the case where the compounding ratio of the silicone compound is larger than 10 parts by mass. This is because the silicone compound is easily mixed evenly with the polyolefin resin, and it is difficult for partial lump formation to occur.
- the blending ratio of the silicone compound to 100 parts by mass of the polyolefin resin is more preferably 8 parts by mass or less, and the blending ratio of the silicone compound to 100 parts by mass of the polyolefin resin is particularly preferably less than 5 parts by mass. In this case, compared with the case where the compounding ratio of the silicone compound is 5 parts by mass or more, more excellent mechanical properties can be obtained in the flame retardant resin composition.
- the blending ratio of the silicone compound to 100 parts by mass of the polyolefin resin is more preferably 4 parts by mass or less. In this case, compared with the case where the compounding ratio of the silicone compound with respect to 100 parts by mass of the polyolefin resin exceeds 4 parts by mass, more excellent mechanical characteristics can be obtained in the flame retardant resin composition.
- the silicone compound may be attached in advance to the surface of calcium carbonate. In this case, segregation of the silicone compound is less likely to occur in the flame retardant resin composition, and the uniformity of characteristics in the flame retardant resin composition is further improved.
- a silicone compound is added to calcium carbonate and mixed to obtain a mixture, and then the mixture is dried at 40 to 75 ° C. for 10 to 40 minutes.
- the dried mixture can be obtained by grinding with a Henschel mixer, an atomizer or the like.
- the fatty acid-containing compound functions as a flame retardant aid.
- the fatty acid-containing compound refers to a compound containing a fatty acid or a metal salt thereof.
- a fatty acid having 12 to 28 carbon atoms is used as the fatty acid.
- examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, tuberculostearic acid, oleic acid, linoleic acid, arachidonic acid, behenic acid and montanic acid.
- stearic acid or tuberculostearic acid is preferable, and stearic acid is particularly preferable. In this case, more excellent flame retardancy can be obtained in the flame retardant resin composition than in the case of using a fatty acid other than stearic acid or tuberculostearic acid.
- the fatty acid-containing compound is preferably a fatty acid metal salt.
- the metal constituting the metal salt of fatty acid include alkaline earth metals such as magnesium and calcium, zinc and lead.
- the fatty acid metal salt magnesium stearate or calcium stearate is preferable. In this case, compared with the case where fatty acid metal salts other than magnesium stearate and calcium stearate are used, more excellent flame retardancy can be obtained with a smaller addition amount in the flame retardant resin composition.
- the fatty acid-containing compound is blended at a ratio of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.
- the flame retardance more excellent in the flame-retardant resin composition is obtained as compared with the case where the proportion of the fatty acid-containing compound is less than 3 parts by mass.
- the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the polyolefin-based resin is within the above range, bleeding occurs as compared with the case where the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the polyolefin-based resin is larger than 20 parts by mass. It becomes difficult.
- the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the polyolefin-based resin is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably less than 5 parts by mass.
- the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the polyolefin-based resin is within the above range, it is more excellent in the flame retardant resin composition than when the blending ratio exceeds the upper limit value of each of the above ranges. Mechanical properties are obtained.
- the fatty acid-containing compound may be previously attached to the surface of calcium carbonate. In this case, segregation of the fatty acid-containing compound is less likely to occur in the flame retardant resin composition, and the uniformity of characteristics in the flame retardant resin composition is further improved. Further, a fatty acid-containing compound and a silicone compound may be attached in advance to the surface of calcium carbonate. In this case, segregation of the silicone compound and the fatty acid-containing compound is less likely to occur in the flame retardant resin composition, and the uniformity of characteristics in the flame retardant resin composition is further improved.
- a silicone compound and a fatty acid-containing compound are added to calcium carbonate and mixed to obtain a mixture. And dried for 10 to 40 minutes, and the dried mixture is pulverized with a Henschel mixer, an atomizer or the like.
- the calcium carbonate may be either heavy calcium carbonate or light calcium carbonate.
- the average particle diameter of calcium carbonate is not particularly limited, but is preferably 1.2 to 1.8 ⁇ m. In this case, it is possible to ensure more excellent flame retardancy in the flame retardant resin composition, and it is possible to ensure better mechanical properties.
- Calcium carbonate is blended at a ratio of 10 parts by mass or more and less than 120 parts by mass with respect to 100 parts by mass of the polyolefin resin. In this case, the flame retardance more excellent in the flame retardant resin composition is obtained compared with the case where the proportion of calcium carbonate is less than 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- the flame retardant resin is more than when the blending ratio of calcium carbonate with respect to 100 parts by mass of the polyolefin resin is 120 parts by mass or more.
- the mechanical properties of the composition can be further improved.
- the blending ratio of calcium carbonate with respect to 100 parts by mass of polyolefin resin is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less.
- a mechanical characteristic can be improved more fully in a flame-retardant resin composition.
- the blending ratio of calcium carbonate with respect to 100 parts by mass of the polyolefin-based resin is preferably 10 parts by mass or more and 80 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less.
- the flame retardancy of the flame retardant resin composition is more sufficiently compared to the case where the blending ratio exceeds the upper limit value of each of the above ranges. While ensuring, mechanical characteristics can be improved more sufficiently.
- the blending ratio of calcium carbonate to 100 parts by mass of the polyolefin resin may be 20 parts by mass or more.
- the silicone compound when blended at a ratio of 1.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the polyolefin resin, the fatty acid-containing compound is based on 100 parts by mass of the polyolefin resin. It is preferable to mix
- Triazine ring-containing hindered amine compound is not particularly limited as long as it contains an oxygen atom in the molecule, but the triazine ring-containing hindered amine compound has a group represented by the following formula (1). It is preferable that it is a compound which has.
- R 1 to R 4 each independently represents an alkyl group having 1 to 8 carbon atoms
- R 5 represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms.
- examples of the alkyl group represented by R 1 to R 4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
- the “alkyl group” includes not only an unsubstituted alkyl group but also a substituted alkyl group.
- the substituted alkyl group those obtained by substituting the hydrogen atom of the unsubstituted alkyl group with a halogen atom such as chlorine can be used.
- examples of the alkyl group represented by R 5 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group.
- Examples of the cycloalkyl group represented by R 5 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.
- Examples of the aralkyl group represented by R 5 include a benzyl group (phenylmethyl group), a phenylethyl group, a phenylpropyl group, a diphenylmethyl group, and a triphenylmethyl group.
- Examples of the aryl group represented by R 5 include a phenyl group and a naphthyl group.
- R 1 to R 4 each independently represents an alkyl group having 1 to 3 carbon atoms
- R 5 represents a cycloalkyl group having 5 to 8 carbon atoms.
- Examples of the triazine ring-containing hindered amine compound having a group represented by the above formula (1) include a compound represented by the following formula (2).
- R 6 to R 8 each independently represents a group represented by the following formula (3)
- R 9 and R 10 each independently represent a group represented by the above formula (1)
- R 11 and R 12 each independently represents an alkyl group having 1 to 18 carbon atoms.
- Examples of the alkyl group represented by R 11 and R 12 include the same alkyl group as the alkyl group represented by R 5 in the above formula (1).
- the triazine ring-containing hindered amine compound is a compound represented by the above formula (2), wherein R 1 to R 4 in the formula (1) each independently represents an alkyl group having 1 to 3 carbon atoms, and R 5 Represents a cycloalkyl group having 5 to 8 carbon atoms, and a compound in which R 11 and R 12 in formula (3) represent an alkyl group having 1 to 6 carbon atoms is preferable. In this case, more excellent flame retardancy is obtained in the flame retardant resin composition.
- triazine ring-containing hindered amine compound examples include compounds represented by the above formula (2), in which R 1 to R 4 in the formula (1) are methyl groups, R 5 is a cyclohexyl group, and in the formula (3) R 11 and R 12 are each represented by a butyl group, R 6 to R 8 are identical to each other, and R 9 and R 10 are identical to each other (trade name “Flamestab NOR 116FF”, manufactured by BASF), the above formula And a compound having a group represented by (1) and a group represented by the above formula (3) (trade name “CYASORB UV-3529”, manufactured by Sun Chemical Co., Ltd.).
- the triazine ring-containing hindered amine compound is blended at a ratio of 0.05 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- the flame retardant resin composition As compared with the case where the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is less than 0.05 parts by mass.
- the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is within the above range, the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is 10 parts by mass or more.
- the mechanical properties and flame retardancy of the flame retardant resin composition can be further improved.
- the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is preferably 0.1 parts by mass or more. In this case, more excellent flame retardancy can be obtained in the flame retardant resin composition as compared with the case where the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is less than 0.1 parts by mass.
- the blending ratio of the triazine ring-containing hindered amine compound to 100 parts by mass of the polyolefin resin is preferably 3 parts by mass or less, and more preferably 1 part by mass or less.
- the flame retardant resin composition can ensure flame retardancy and have more excellent mechanical properties.
- the flame retardant resin composition may further contain a filler such as an antioxidant, an ultraviolet degradation inhibitor, a processing aid, a color pigment, a lubricant, and carbon black as necessary.
- a filler such as an antioxidant, an ultraviolet degradation inhibitor, a processing aid, a color pigment, a lubricant, and carbon black as necessary.
- the flame retardant resin composition can be obtained by kneading a polyolefin resin, a silicone compound, a fat-containing compound, calcium carbonate, a triazine ring-containing hindered amine compound, and the like.
- the kneading can be performed with a kneading machine such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, a twin screw extruder, a mixing roll, and the like.
- a part of the polyolefin resin and the silicone compound are kneaded, and the obtained master batch (MB) is mixed with the remaining polyolefin resin and fatty acid-containing compound. Further, it may be kneaded with calcium carbonate and a triazine ring-containing hindered amine compound.
- the inner conductor 1 is covered with the flame retardant resin composition.
- the flame retardant resin composition is melt kneaded using an extruder to form a tubular extrudate. Then, the tubular extrudate is continuously coated on the inner conductor 1. Thus, the insulated wire 4 is obtained.
- ⁇ Coat> Finally, one insulated wire 4 obtained as described above is prepared, and this insulated wire 4 is covered with a jacket 3 made using the above-mentioned flame-retardant resin composition.
- the outer jacket 3 is a so-called sheath and protects the insulator 2 from physical or chemical damage.
- the present invention is not limited to the above embodiment.
- the round cable 10 having one insulated wire 4 is used as the cable.
- the cable of the present invention is not limited to the round cable, and is insulated inside the jacket 3.
- a cable having two or more electric wires 4 may be used.
- a resin portion made of polypropylene or the like may be provided between the jacket 3 and the insulated wire 4.
- the insulator 2 and the jacket 3 of the insulated wire 4 are comprised with said flame-retardant resin composition
- the insulator 2 is comprised with normal insulation resin, and only the jacket 3 is The flame retardant resin composition may be used.
- the insulator 2 is not necessarily required and can be omitted.
- FIG. 3 is a cross-sectional view showing a drop-type optical fiber cable as an example of an optical fiber cable.
- the optical fiber cable 20 includes a support wire 21, two tension members 22 and 23, an optical fiber 24, and an outer sheath 25 as an insulator covering them.
- the jacket 25 is comprised with the flame-retardant resin composition which comprises the insulator 2 and the jacket 3 of the insulated wire 4 in the said embodiment.
- the flame retardant resin composition of the present invention is not only applicable to the above-mentioned cable and optical fiber cable insulators, but various flame retardant properties such as tubes, tapes, packaging materials, and building materials are required. It can also be applied to applications.
- Examples 1 to 88 and Comparative Examples 1 to 54 A polyolefin resin, a silicone masterbatch (silicone MB), a fatty acid-containing compound, calcium carbonate, and a triazine ring-containing hindered amine compound (HALS) are blended in the blending amounts shown in Tables 1 to 25, and 15 at 160 ° C. with a Banbury mixer. Kneading for a minute gave a flame retardant resin composition.
- the unit of the blending amount of each blending component is part by mass.
- the blending amount in the polyolefin resin column may not be 100 parts by mass. In that case, the blending amount of the polyolefin resin and the polyethylene (PE) contained in the silicone MB The total blending amount is 100 parts by mass.
- polyolefin resin silicone MB
- calcium carbonate calcium carbonate
- fatty acid-containing compound fatty acid-containing compound
- HALS HALS
- Polyolefin resin (1-1) Polyethylene (PE) Product name “Excellen GMH GH030”, manufactured by Sumitomo Chemical Co., Ltd. (1-2) acid-modified polyethylene (acid-modified PE) Trade name "Toughmer MA8510", Mitsui Chemicals (1-3) polypropylene (PP) Product name “J-452HP”, Prime Polymer Co., Ltd. (1-4) ethylene ethyl acrylate copolymer (EEA) Product name “Lex Pearl A1150”, manufactured by Nippon Polyethylene (1-5) ethylene vinyl acetate copolymer (EVA) Product name "Evaflex EV150”, Mitsui DuPont Polychemical Co., Ltd.
- PE Polyethylene
- EVA ethylene vinyl acetate copolymer
- SEBS styrene ethylene butadiene styrene copolymer
- SBR styrene butadiene rubber
- HALS (6-1) HALS1
- R 1 to R 4 in the formula (1) are methyl groups
- R 5 is a cyclohexyl group
- R 11 and R 12 in the formula (3) are butyl groups
- a conductor (number of strands / cross-sectional area of 2 mm 2 ) was coated to a thickness of 0.7 mm. Thus, an insulated wire was obtained.
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Abstract
Description
(上記式(2)において、R6~R8は各々独立に、下記式(3)で表される基を表す)
(上記式(3)において、R9及びR10は各々独立に、上記式(1)で表される基を表し、R11及びR12は各々独立に、炭素数1~18のアルキル基を表す)
図1は、本発明に係るケーブルの一実施形態を示す部分側面図である。図2は、図1のII-II線に沿った断面図である。図1及び図2に示すように、丸型ケーブル10は、絶縁電線4と、絶縁電線4を被覆する絶縁体としてのチューブ状の外被3とを備えている。そして、絶縁電線4は、導体としての内部導体1と、内部導体1を被覆するチューブ状の絶縁体2とを有している。すなわち、丸型ケーブル10はメタルケーブルであり、丸型ケーブル10では、内部導体1は、チューブ状の絶縁体2の内側に設けられるとともにチューブ状の外被3の内側に設けられている。
次に、上述した丸型ケーブル10の製造方法について説明する。
まず導体としての内部導体1を準備する。内部導体1は、1本の素線のみで構成されてもよく、複数本の素線を束ねて構成されたものであってもよい。また、内部導体1は、導体径や導体の材質などについて特に限定されるものではなく、用途に応じて適宜定めることができる。内部導体1としては、銅などの金属を用いることができる。
一方、上記難燃性樹脂組成物を準備する。難燃性樹脂組成物は、上述したように、ポリオレフィン系樹脂と、シリコーン系化合物と、脂肪酸含有化合物と、炭酸カルシウムと、トリアジン環含有ヒンダードアミン系化合物とを含む。
ポリオレフィン系樹脂としては、例えばポリエチレン(PE)、酸変性ポリエチレン、エチレン-酢酸ビニル共重合体(EVA)、エチレン-アクリル酸エチル共重合体(EEA)、ポリプロピレン(PP)、エチレン-アクリル酸メチル共重合体(EMA)、エチレン-プロピレン共重合体、エチレン-ブテン共重合体、エチレン-ヘキセン共重合体、エチレン-オクテン共重合体及びオレフィン系熱可塑性エラストマーなどが挙げられる。これらは単独で又は2種以上を組み合せて用いることができる。中でも、ポリオレフィン系樹脂は、ポリエチレン、酸変性ポリエチレン、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エチル共重合体及びポリプロピレンからなる群より選ばれる少なくとも1種で構成されることが好ましい。
シリコーン系化合物は、難燃助剤として機能するものであり、シリコーン系化合物としては、ポリオルガノシロキサンなどが挙げられる。ここで、ポリオルガノシロキサンは、シロキサン結合を主鎖に有し、側鎖に有機基を有するものである。有機基としては、例えばメチル基、エチル基、プロピル基、ブチル基などのアルキル基、ビニル基、フェニル基、ナフチル基などのアリール基などが挙げられる。具体的にはポリオルガノシロキサンとしては、例えばジメチルポリシロキサン、メチルエチルポリシロキサン、メチルオクチルポリシロキサン、メチルビニルポリシロキサン、メチルフェニルポリシロキサン、メチル(3,3,3-トリフルオロプロピル)ポリシロキサンなどが挙げられる。ポリオルガノシロキサンは、シリコーンオイル、シリコーンパウダー、シリコーンガム又はシリコーンレジンの形態で用いられる。中でも、ポリオルガノシロキサンは、シリコーンガムの形態で用いられることが好ましい。この場合、ブルームが起こりにくくなる。
脂肪酸含有化合物は、難燃助剤として機能するものである。脂肪酸含有化合物とは、脂肪酸又はその金属塩を含有するものを言う。ここで、脂肪酸としては、例えば炭素原子数が12~28である脂肪酸が用いられる。このような脂肪酸としては、例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ツベルクロステアリン酸、オレイン酸、リノール酸、アラキドン酸、ベヘン酸及びモンタン酸が挙げられる。中でも、脂肪酸としては、ステアリン酸又はツベルクロステアリン酸が好ましく、ステアリン酸が特に好ましい。この場合、ステアリン酸又はツベルクロステアリン酸以外の脂肪酸を用いる場合に比べて、難燃性樹脂組成物においてより優れた難燃性が得られる。
炭酸カルシウムは、重質炭酸カルシウム又は軽質炭酸カルシウムのいずれでもよい。
トリアジン環含有ヒンダードアミン系化合物は、分子内に酸素原子を含んでいれば特に制限されないが、トリアジン環含有ヒンダードアミン系化合物は下記式(1)で表される基を有する化合物であることが好ましい。
最後に、上記のようにして得られた絶縁電線4を1本用意し、この絶縁電線4を、上述した難燃性樹脂組成物を用いて作製した外被3で被覆する。外被3は、いわゆるシースであり、絶縁体2を物理的又は化学的な損傷から保護するものである。
ポリオレフィン系樹脂、シリコーンマスターバッチ(シリコーンMB)、脂肪酸含有化合物、炭酸カルシウム及びトリアジン環含有ヒンダードアミン系化合物(HALS)を、表1~25に示す配合量で配合し、バンバリーミキサによって160℃にて15分間混練し、難燃性樹脂組成物を得た。なお、表1~25において、各配合成分の配合量の単位は質量部である。また表1~25において、ポリオレフィン系樹脂の欄の配合量が100質量部となっていない場合があるが、その場合には、ポリオレフィン系樹脂の配合量とシリコーンMB中に含まれるポリエチレン(PE)の配合量とを合計すればその合計配合量は100質量部となる。
(1-1)ポリエチレン(PE)
商品名「エクセレン GMH GH030」、住友化学社製
(1-2)酸変性ポリエチレン(酸変性PE)
商品名「タフマーMA8510」、三井化学社製
(1-3)ポリプロピレン(PP)
商品名「J-452HP」、プライムポリマー社製
(1-4)エチレンエチルアクリレート共重合体(EEA)
商品名「レクスパールA1150」、日本ポリエチレン社製
(1-5)エチレン酢酸ビニル共重合体(EVA)
商品名「エバフレックスEV150」、三井・デュポン・ポリケミカル社製
(1-6)スチレンエチレンブタジエンスチレン共重合体(SEBS)
商品名「タフテックM1913」、旭化成ポリケミカルズ社製
(1-7)スチレンブタジエンゴム(SBR)
商品名「ダイナロン1320P」、JSR社製
商品名「X-22-2125H」、信越化学社製
(50質量%シリコーンガムと50質量%PEとを含有)
商品名「KF-96-350cs」、信越化学社製
商品名「NCC-P」、日東粉化社製、平均粒径1.7μm
(5-1)ステアリン酸Mg
商品名「エフコケムMGS」、ADEKA社製
(5-2)ステアリン酸Zn
商品名「ジンクステアレートG」、日油社製
(6-1)HALS1
式(2)で表される化合物であって式(1)におけるR1~R4がメチル基、R5がシクロヘキシル基、式(3)におけるR11及びR12がブチル基で表され、R6~R8が互いに同一であり、R9及びR10が互いに同一である化合物
商品名「Flamestab NOR 116FF」、BASF社製
(6-2)HALS2
商品名「CYASORB UV-3529」、サンケミカル社製
実施例1~88及び比較例1~54の各々で得られた10本の絶縁電線について、JIS C3665-1に準拠した垂直一条燃焼試験を行った。そして、10本の絶縁電線のうち、下記(1A)及び(2A)の条件をいずれも満たす絶縁電線の割合を合格率(単位:%)として下記式(3A)に基づいて算出した。結果を表1~25に示す。なお、表1~25において、難燃性の合否基準は以下の通りとした。
(1A)絶縁電線を上部で支持する上部支持材の下端と炭化開始点との距離が50mm以上であり且つ絶縁電線において燃焼が上部支持材の下端から540mmより下方に広がらなかった
(2A)除炎から自己消火までの時間が60秒以下である
合格率(%)=100×上記(1A)及び(A2)の基準をいずれも満たした絶縁電線の本数/試験を行った絶縁電線の総数(10本)・・・(3A)
合格 :合格率80%以上
不合格:合格率80%未満
機械的特性の評価は、実施例1~88及び比較例1~54の絶縁電線について、JIS C3005により引張試験を行い、測定された引張強度に基づいて行った。結果を表1~25に示す。表1~25において、引張強度の単位はMPaであり、引張強度の合否基準は下記の通りとした。なお、引張試験において、引張速度は200mm/min、標線間距離は20mmとした。
10MPa以上:合格
10MPa未満:不合格
2…絶縁体
3…外被(絶縁体)
4…絶縁電線
10…丸型ケーブル(ケーブル)
20…光ファイバケーブル
24…光ファイバ
25…外被(絶縁体)
Claims (10)
- ポリオレフィン系樹脂と、
シリコーン系化合物と、
脂肪酸含有化合物と、
炭酸カルシウムと、
トリアジン環含有ヒンダードアミン系化合物とを含み、
前記シリコーン系化合物が、前記ポリオレフィン系樹脂100質量部に対して1.5質量部以上10質量部以下の割合で配合され、
前記脂肪酸含有化合物が、前記ポリオレフィン系樹脂100質量部に対して3質量部以上20質量部以下の割合で配合され、
前記炭酸カルシウムが、前記ポリオレフィン系樹脂100質量部に対して10質量部以上120質量部未満の割合で配合され、
前記トリアジン環含有ヒンダードアミン系化合物が、前記ポリオレフィン系樹脂100質量部に対して0.05質量部以上10質量部未満の割合で配合され、
前記トリアジン環含有ヒンダードアミン系化合物が酸素原子を含む難燃性樹脂組成物。 - 前記トリアジン環含有ヒンダードアミン系化合物が、前記ポリオレフィン系樹脂100質量部に対して0.1質量部以上10質量部未満の割合で配合される請求項1に記載の難燃性樹脂組成物。
- 前記式(1)において、R1~R4が各々独立に、炭素数1~3のアルキル基を表し、R5がシクロアルキル基を表す、請求項3に記載の難燃性樹脂組成物。
- 前記トリアジン環含有ヒンダードアミン系化合物が、前記式(2)で表される化合物であって前記式(1)におけるR1~R4が各々独立に、炭素数1~3のアルキル基を表し、R5が炭素数5~8のシクロアルキル基を表し、前記式(3)におけるR11及びR12が炭素数1~6のアルキル基を表す化合物で構成される、請求項5に記載の難燃性樹脂組成物。
- 前記シリコーン系化合物が、前記ポリオレフィン系樹脂100質量部に対して1.5質量部以上5質量部未満の割合で配合され、
前記脂肪酸含有化合物が、前記ポリオレフィン系樹脂100質量部に対して3質量部以上5質量部未満の割合で配合され、
前記炭酸カルシウムが、前記ポリオレフィン系樹脂100質量部に対して10質量部以上40質量部以下の割合で配合される請求項1~6のいずれか一項に記載の難燃性樹脂組成物。 - 前記ポリオレフィン系樹脂が、ポリエチレン、酸変性ポリエチレン、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エチル共重合体及びポリプロピレンからなる群より選ばれる少なくとも1種で構成される請求項1~7のいずれか一項に記載の難燃性樹脂組成物。
- 導体と、
前記導体を被覆する少なくとも1つの絶縁体とを備え、
前記絶縁体が、請求項1~8のいずれか一項に記載の難燃性樹脂組成物で構成されるケーブル。 - 光ファイバと、
前記光ファイバを被覆する絶縁体とを有する光ファイバケーブルであって、
前記絶縁体が、請求項1~8のいずれか一項に記載の難燃性樹脂組成物で構成される光ファイバケーブル。
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CN115926338A (zh) * | 2022-11-07 | 2023-04-07 | 盐城幼儿师范高等专科学校 | 一种环保pvc装饰板及其制造工艺 |
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