WO2023234581A1 - Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci - Google Patents
Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci Download PDFInfo
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- WO2023234581A1 WO2023234581A1 PCT/KR2023/006365 KR2023006365W WO2023234581A1 WO 2023234581 A1 WO2023234581 A1 WO 2023234581A1 KR 2023006365 W KR2023006365 W KR 2023006365W WO 2023234581 A1 WO2023234581 A1 WO 2023234581A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- thermoplastic resin
- resin composition
- weight
- flame retardant
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 53
- 239000003063 flame retardant Substances 0.000 claims abstract description 64
- 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 claims abstract description 56
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 33
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 29
- 229920000554 ionomer Polymers 0.000 claims abstract description 26
- 239000003365 glass fiber Substances 0.000 claims abstract description 23
- 238000002834 transmittance Methods 0.000 claims abstract description 20
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- -1 diethyl phosphinate ammonium salt Chemical class 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 7
- 229920000388 Polyphosphate Polymers 0.000 claims description 7
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical group [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 7
- 239000001205 polyphosphate Substances 0.000 claims description 7
- 235000011176 polyphosphates Nutrition 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 3
- 229920006396 polyamide 1012 Polymers 0.000 claims description 3
- 229920006394 polyamide 410 Polymers 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- ZVMAGJJPTALGQB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC(OCC(O)=O)=C1 ZVMAGJJPTALGQB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the present invention relates to thermoplastic resin compositions and molded articles manufactured therefrom.
- Thermoplastic resin compositions used in automobile parts or electrical appliances have industrial standards for flame retardancy and require excellent electrical insulation and flame retardancy.
- governments in each country are supporting the distribution of electric vehicles, and as a result, demand for electric vehicle batteries is increasing.
- flame retardancy in thin films of thermoplastic resin compositions is gaining importance.
- Polyamide resin provides excellent heat resistance and moldability, so it is useful in automobile parts or electrical appliances.
- polyamide resins lack flame resistance, so flame retardants must be added to provide the flame retardancy required for specific applications.
- Bromine-based compounds and antimony-based compounds may be used as the flame retardant, but especially when bromine-based compounds are used as flame retardants, bromine-based compounds and antimony-based compounds are included because they may cause environmental problems when a resin composition containing them is burned. If so, its use may be limited.
- phosphorus-based flame retardants are being used to improve the flame retardancy of polyamide resin compositions.
- the laser transmittance of polyamide resin compositions containing them and molded products manufactured therefrom decreases, resulting in component parts using laser welding technology. It is difficult to join them.
- thermoplastic resin composition that is flame retardant and also has excellent laser transmittance.
- the purpose of the present invention is to provide a thermoplastic resin composition with excellent flame retardancy, impact resistance, fluidity, and laser transmittance.
- Another object of the present invention is to provide a molded article manufactured from the thermoplastic resin composition.
- thermoplastic resin composition includes (A) about 40 to about 70% by weight of polyamide resin; (B) about 5 to about 10 weight percent of a phosphorus-based flame retardant; (C) about 2 to about 5% by weight of a melamine-based flame retardant; and (D) about 20 to about 50% by weight of glass fiber; (E) about 0.5 to about 3 parts by weight of zinc borate; and (F) about 1 to about 3 parts by weight of an ionomer.
- the polyamide resin is polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6I, polyamide 6T, poly It may include amide 4T, polyamide 410, polyamide 510, polyamide 1010, polyamide 1012, polyamide 10T, polyamide 1212, polyamide 12T, polyamide MXD6, or a combination thereof.
- the polyamide resin may be polyamide 66.
- the phosphorus-based flame retardant is aluminum diethyl phosphinate, triphenyl phosphate, ammonium polyphosphate, resorcinol-di(bis- 2,6-dimethylphenyl) phosphate (resorcinol-di(bis-2,6-dimethylphenyl) phosphate), bisphenol A diphenyl phosphate, cyclophosphazene, diethyl phosphinate ammonium salt ( diethyl phosphinate ammonium salt), or any combination thereof.
- the phosphorus-based flame retardant may be aluminum diethyl phosphinate.
- the melamine-based flame retardant may be any one of melamine polyphosphate, melamine phosphate, melamine pyrophosphate, or a combination thereof.
- the melamine-based flame retardant may be melamine polyphosphate.
- the ionomer may be one in which the carboxylic acid of methacrylic acid is neutralized with a metal ion in the molecule of an ethylene-methacrylic acid copolymer in which ethylene and methacrylic acid are copolymerized.
- the weight average molecular weight of the ionomer may be about 10,000 to about 100,000 g/mol.
- thermoplastic resin composition is selected from antibacterial agents, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, pigments, and dyes. At least one additional additive may be included.
- the molded article is manufactured from the thermoplastic resin composition according to any one of items 1 to 10 above.
- the molded product may have a flame resistance of V-0 or higher as measured on a 1.5 mm thick specimen according to the UL94 standard.
- the molded article may have a laser transmittance of about 20 to about 50% at a wavelength of 980 nm for a 1.5 mm thick specimen.
- the molded article may have an Izod impact strength of about 8 kgf ⁇ cm/cm or more as measured on a 1/8 inch thick specimen according to the ASTM D256 standard.
- the molded article may have a flow index of about 85 g/10min or more as measured at 275°C and a load of 2.16 kg according to the ASTM D1238 standard.
- thermoplastic resin composition includes (A) polyamide resin; (B) phosphorus-based flame retardant; (C) melamine-based flame retardant; (D) glass fiber; (E) zinc borate; and (F) ionomer.
- copolymerization means block copolymerization, random copolymerization, and graft copolymerization
- copolymer means block copolymer, random copolymer, and graft copolymerization
- the polyamide resin according to one embodiment of the present invention enables the thermoplastic resin composition to realize excellent mechanical properties.
- the polyamide resin may be a variety of polyamide resins known in the art, for example, aromatic polyamide resin, aliphatic polyamide resin, or mixtures thereof, and is not particularly limited.
- the aromatic polyamide resin is a polyamide resin containing an aromatic group in the main chain, and may be a wholly aromatic polyamide resin, a semi-aromatic polyamide resin, or a mixture thereof.
- the wholly aromatic polyamide resin refers to a polymer of an aromatic diamine and an aromatic dicarboxylic acid
- the semi-aromatic polyamide resin includes at least one aromatic unit and at least one non-aromatic unit between amide bonds.
- the semi-aromatic polyamide resin may be a polymer of aromatic diamine and aliphatic dicarboxylic acid, or may be a polymer of aliphatic diamine and aromatic dicarboxylic acid.
- the aliphatic polyamide resin refers to a polymer of aliphatic diamine and aliphatic dicarboxylic acid.
- examples of the aromatic diamine include p-xylene diamine, m-xylene diamine, etc., but are not limited thereto. Additionally, these may be used alone or in combination of two or more types.
- examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, (1,3-phenylenedioxy)diacetic acid, etc. It is not limited. Additionally, these may be used alone or in combination of two or more types.
- examples of the aliphatic diamine include ethylenediamine, trimethylenediamine, hexamethylenediamine, dodecamethylenediamine, piperazine, etc., but are not limited thereto. Additionally, these may be used alone or in combination of two or more types.
- examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. It is not limited to this. Additionally, these may be used alone or in combination of two or more types.
- the polyamide resin is polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6I, polyamide 6T, polyamide 4T, polyamide 410, polyamide 510, polyamide 1010, polyamide 1012, polyamide 10T, polyamide 1212, polyamide 12T, polyamide MXD6, or a combination thereof.
- the polyamide resin may be polyamide 66.
- the polyamide resin is about 40 to about 70% by weight of 100% by weight of the basic material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber). , for example, about 50 to about 70% by weight, for example, about 50 to about 60% by weight.
- the thermoplastic resin composition and molded articles manufactured therefrom can exhibit excellent mechanical properties due to the polyamide resin.
- the phosphorus-based flame retardant according to one embodiment of the present invention is used together with the melamine-based flame retardant described later to enhance the flame retardancy of the thermoplastic resin composition and achieve a high level of flame retardancy.
- the phosphorus-based flame retardant a typical phosphorus-based flame retardant used to reinforce the flame retardancy of a thermoplastic resin composition can be used.
- the phosphorus-based flame retardant is a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphazene compound, or these.
- Metal salts, etc. can be used.
- the phosphorus-based flame retardants can be used alone or in combination of two or more types.
- the phosphorus-based flame retardant is aluminum diethyl phosphinate, triphenyl phosphate, ammonium polyphosphate, resorcinol-di(bis-2,6-dimethylphenyl) ) phosphate (resorcinol-di(bis-2,6-dimethylphenyl) phosphate), bisphenol A diphenyl phosphate, cyclophosphazene, diethyl phosphinate ammonium salt, Or it may include a combination thereof.
- the phosphorus-based flame retardant may be aluminum diethyl phosphinate.
- the phosphorus-based flame retardant is about 5 to about 10% by weight, based on 100% by weight of the base material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber).
- the base material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber).
- the thermoplastic resin composition may have excellent flame retardancy and, at the same time, excellent mechanical properties and moldability.
- the melamine-based flame retardant according to one embodiment of the present invention is used together with the phosphorus-based flame retardant to enhance the flame retardancy of the thermoplastic resin composition and achieve a high level of flame retardancy.
- a typical melamine-based flame retardant used to reinforce the flame retardancy of a thermoplastic resin composition can be used.
- the melamine-based flame retardant may include melamine polyphosphate, melamine phosphate, melamine pyrophosphate, or a combination thereof.
- the melamine-based flame retardant may be melamine polyphosphate.
- the melamine-based flame retardant is about 2 to about 5% by weight based on 100% by weight of the base material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber). , for example, may be included in about 2 to about 3% by weight.
- the thermoplastic resin composition may have excellent flame retardancy and, at the same time, excellent mechanical properties and moldability.
- Glass fiber according to one embodiment of the present invention not only improves mechanical properties such as tensile strength of a thermoplastic resin composition, but also plays a role in improving flame retardancy.
- glass fiber glass fiber used in conventional thermoplastic resin compositions can be used.
- the average diameter of the glass fibers may range from about 1 to about 20 ⁇ m, such as from about 1 to about 15 ⁇ m, such as from about 1 to about 10 ⁇ m, such as from about 1 to about 5 ⁇ m. It may be ⁇ m, but is not limited thereto.
- the average length of the glass fibers before processing may be less than or equal to about 10 mm, such as about 1 to about 8 mm, such as about 1 to about 5 mm, such as about 1 to about 3 mm. However, it is not limited to this. When the average diameter and average length of the glass fiber are within the above range, mechanical properties, etc. may be excellent.
- the glass fiber may have a circular, oval, rectangular, or dumbbell-shaped cross-section, and two or more types with different cross-sectional shapes, average diameters, and average lengths may be used as a mixture. there is.
- the surface of the glass fiber may be treated with a certain surface treatment agent to improve adhesion between the glass fiber and the thermoplastic resin.
- a certain surface treatment agent to improve adhesion between the glass fiber and the thermoplastic resin.
- the fluidity and impact strength of the thermoplastic resin composition may vary.
- silane-based compounds, epoxy-based compounds, and urethane-based compounds may be used as the surface treatment agent, and commonly commercialized surface treatment agents may be used without limitation.
- the glass fiber is about 20 to about 50% by weight of 100% by weight of the basic material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber).
- the basic material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber).
- it may be included in about 20 to about 40% by weight, for example, about 30 to about 40% by weight.
- the thermoplastic resin composition and molded articles manufactured therefrom may exhibit excellent mechanical properties and flame retardancy.
- Zinc borate according to one embodiment of the present invention can improve the flame retardancy of a thermoplastic resin composition.
- the amount of zinc borate is about 0.5 to about 3 parts by weight based on about 100 parts by weight of the base material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber). It may be included in parts by weight, for example, about 0.5 to about 2 parts by weight. Within the above range, the flame retardancy of the thermoplastic resin composition and molded products using the same may be excellent.
- the ionomer according to one embodiment of the present invention can provide excellent laser transmittance to a thermoplastic resin composition.
- An ionomer generally refers to a material containing a small amount of ionic groups in the chain of a non-polar polymer resin, and the structure, physical properties, morphology, etc. of the polymer resin can be controlled by introducing ionic groups into the polymer structure.
- the ionomer may include at least one of ethylene, methacrylic acid, or acrylate derivatives and a metal ion in the repeating unit.
- the ionomer can be synthesized by bridging a copolymer of ethylene and methacrylic acid with a metal ion, and the ionomer can be synthesized by bridging a terpolymer of ethylene, methacrylic acid, and acrylate with a metal ion. can also be synthesized.
- the ionomer is one in which the carboxylic acid of methacrylic acid is neutralized with a metal ion in the molecule of ethylene-methacrylic acid copolymer. ) can be used.
- the ionomer may be an ionomer having a repeating unit neutralized with sodium ions as represented by the following formula (1).
- m and n are integers from 2 to 30,000.
- the ionomer has a weight average molecular weight measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g/mol, for example, about 30,000 to about 100,000 g/mol, for example It may be about 50,000 to about 100,000 g/mol.
- GPC gel permeation chromatography
- the ionomer is used in an amount of about 1 to about 3, based on about 100 parts by weight of the base material ((A) polyamide resin, (B) phosphorus-based flame retardant, (C) melamine-based flame retardant, and (D) glass fiber). It may be included in parts by weight, for example, about 1 to about 2 parts by weight.
- the thermoplastic resin composition and molded articles manufactured therefrom can exhibit excellent laser transmittance.
- the additive may be at least one selected from antibacterial agents, nucleating agents, coupling agents, fillers, plasticizers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, pigments, and dyes.
- these additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition.
- they may be included in an amount of about 20 parts by weight or less based on about 100 parts by weight of the base material, but are limited thereto. It doesn't work.
- thermoplastic resin composition can also be used by mixing with other resins or other rubber components.
- the molded article according to the present invention is manufactured from the above thermoplastic resin composition.
- the thermoplastic resin composition can be manufactured in the form of pellets, etc., and the manufactured pellets can be manufactured by various methods known in the art, such as injection molding and extrusion molding.
- the molded product may have a flame resistance of V-0 or higher as measured on a 1.5 mm thick specimen according to the UL94 standard.
- the molded article may have a laser transmittance of about 20 to about 50% at a wavelength of 980 nm for a 1.5 mm thick specimen.
- the molded article may have a notched Izod impact strength of about 8 kgf ⁇ cm/cm or more as measured on a 1/8 inch thick specimen according to the ASTM D256 standard.
- the molded article may have a melt-flow index of about 85 g/10min or more as measured at 275°C and a load of 2.16 kg according to the ASTM D1238 standard.
- Polyamide 66 resin (product name: Leona TM 1200) from Ashahi Kasei Corp. was used.
- Aluminum diethylphosphinate (product name: Exolite® OP 1230) from Clariant was used.
- Glass fiber product name: ECS03T-251H manufactured by Nippon Electric Glass was used, with a circular cross-section, a diameter of approximately 10 ⁇ m, an average length before processing of approximately 3 mm, and surface-treated with a urethane-based compound.
- thermoplastic resin composition in the form of a pellet was prepared.
- the thermoplastic resin composition was dried at about 80°C for about 2 hours, and then using a 6 oz injection molding machine, the cylinder temperature was set to about 250°C and the mold temperature was set to about 60°C to prepare a specimen for measuring physical properties.
- the physical properties of the manufactured specimen were evaluated by the following method, and the results are shown in Table 1 below.
- Flame retardancy (unit: grade): The flame retardancy grade was evaluated for 1.5 mm thick specimens according to the UL94 standard.
- Fluidity (unit: g/10min): Melt-flow index (MI) was measured at 275°C and 2.16 kg load according to ASTM D1238 standard.
- Laser transmittance (unit: %): The laser transmittance at a wavelength of 980 nm for a 1.5 mm thick specimen was measured using an Eve Laser laser transmittance meter (product name: ETM-31).
- Parts by weight Parts by weight per 100 parts by weight of basic materials (A, B, C and D)
- thermoplastic resin composition of the present invention has excellent impact resistance (notched Izod impact strength), fluidity (flow index), mechanical properties (tensile strength), and flame retardancy (flame retardant grade), and has excellent laser transmittance of 20% or more. You can confirm that it can be maintained.
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Abstract
Une composition de résine thermoplastique selon la présente invention comprend, par rapport à environ 100 parties en poids d'un matériau de base comprenant (A) environ 40 à 70 % en poids d'une résine de polyamide, (B) environ 5 à 10 % en poids d'un retardateur de flamme à base de phosphore, (C) environ 2 à 5 % en poids d'un retardateur de flamme à base de mélamine, et (D) environ 20 à 50 % en poids de fibre de verre : (E) environ 0,5 à 3 parties en poids de borate de zinc ; et (F) environ 1 à 3 parties en poids d'un ionomère. La composition de résine thermoplastique et un produit moulé fabriqué à partir de celle-ci sont excellents en termes d'ininflammabilité, de résistance aux chocs, de fluidité et de transmittance laser.
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KR1020220067016A KR20230166708A (ko) | 2022-05-31 | 2022-05-31 | 열가소성 수지 조성물 및 이로부터 제조되는 성형품 |
KR10-2022-0067016 | 2022-05-31 |
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Citations (5)
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JP2002201351A (ja) * | 2000-12-22 | 2002-07-19 | E I Du Pont De Nemours & Co | ポリアミド系樹脂組成物およびその成形品 |
KR20100044193A (ko) * | 2007-08-01 | 2010-04-29 | 가부시키가이샤 구라레 | 폴리아미드 조성물 |
CN105062050A (zh) * | 2015-07-17 | 2015-11-18 | 中国科学院理化技术研究所 | 一种耐酸碱无卤阻燃玻璃纤维增强尼龙66复合材料及其制备方法 |
KR20170017807A (ko) * | 2015-08-06 | 2017-02-15 | 이엠에스-패턴트 에이지 | 철로 적용용 난연제 폴리아미드 12 몰딩 조성물 |
KR20170056567A (ko) * | 2014-09-18 | 2017-05-23 | 프라운호퍼 게젤샤프트 쭈르 푀르데룽 데어 안겐반텐 포르슝 에. 베. | 난연제로서 유기 옥시이미드 염의 용도, 난연성 플라스틱 물질 조성물, 이들의 제조 방법, 및 성형 부품, 페인트 또는 코팅 |
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2022
- 2022-05-31 KR KR1020220067016A patent/KR20230166708A/ko unknown
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2023
- 2023-05-10 WO PCT/KR2023/006365 patent/WO2023234581A1/fr unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002201351A (ja) * | 2000-12-22 | 2002-07-19 | E I Du Pont De Nemours & Co | ポリアミド系樹脂組成物およびその成形品 |
KR20100044193A (ko) * | 2007-08-01 | 2010-04-29 | 가부시키가이샤 구라레 | 폴리아미드 조성물 |
KR20170056567A (ko) * | 2014-09-18 | 2017-05-23 | 프라운호퍼 게젤샤프트 쭈르 푀르데룽 데어 안겐반텐 포르슝 에. 베. | 난연제로서 유기 옥시이미드 염의 용도, 난연성 플라스틱 물질 조성물, 이들의 제조 방법, 및 성형 부품, 페인트 또는 코팅 |
CN105062050A (zh) * | 2015-07-17 | 2015-11-18 | 中国科学院理化技术研究所 | 一种耐酸碱无卤阻燃玻璃纤维增强尼龙66复合材料及其制备方法 |
KR20170017807A (ko) * | 2015-08-06 | 2017-02-15 | 이엠에스-패턴트 에이지 | 철로 적용용 난연제 폴리아미드 12 몰딩 조성물 |
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