CN112739765A - Flame-retardant resin composition and molded article - Google Patents
Flame-retardant resin composition and molded article Download PDFInfo
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- CN112739765A CN112739765A CN201980062108.4A CN201980062108A CN112739765A CN 112739765 A CN112739765 A CN 112739765A CN 201980062108 A CN201980062108 A CN 201980062108A CN 112739765 A CN112739765 A CN 112739765A
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- resin composition
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- retardant resin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 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 65
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
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- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 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 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- 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
- C08K5/01—Hydrocarbons
-
- 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
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A flame-retardant resin composition which comprises the following components (A) to (C) in the following amounts, has a melt flow rate at 190 ℃ of 0.05g/10 min to 12g/10 min, and contains substantially no antimony. (A) The polyolefin composition is characterized by comprising (A) 65-98.9% by mass of a polyolefin, (B) 0.1-5% by mass of a radical generator, and (C) 1-30% by mass of a flame retardant.
Description
Technical Field
The present invention relates to a flame-retardant resin composition and a molded article.
Background
Polyolefins are used in a wide range of fields as molding materials because of their excellent properties, but because of their flammability, they are often required to impart flame retardancy when used as industrial materials.
For the purpose of flame retardancy, compositions in which an antimony compound is added to a polyolefin are known (for example, patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-322322
Patent document 2: japanese laid-open patent publication No. 2012-500880
Disclosure of Invention
The purpose of the present invention is to provide a flame-retardant resin composition and a molded article that can suppress the content of antimony and can provide a molded article having excellent flame retardancy.
The present inventors have noticed based on this knowledge that, in the case where the flame-retardant resin composition contains an antimony compound, particularly antimony trioxide, the use is limited because antimony trioxide is a highly toxic substance and a substance specified as a standard for preventing harm of specific chemical substances.
The present inventors have conducted extensive studies and as a result, have found that the content of antimony in a flame-retardant resin composition can be suppressed by setting the melt flow rate of the flame-retardant resin composition to a specific value, and have completed the present invention.
The present invention provides the following flame-retardant resin composition.
1. A flame-retardant resin composition which comprises the following components (A) to (C) in the following amounts, has a melt flow rate at 190 ℃ of 0.05g/10 min to 12g/10 min, and contains substantially no antimony.
(A) A polyolefin in an amount of 65 to 98.9 mass%,
(B) 0.1 to 5% by mass of a radical generator,
(C) the flame retardant is 1 to 30 mass%.
2. The flame-retardant resin composition according to 1, wherein the component (A) has a melt flow rate of 0.1g/10 min or more and less than 15g/10 min at 230 ℃.
3. The flame-retardant resin composition according to claim 1 or 2, wherein the component (A) comprises polypropylene.
4. The flame-retardant resin composition according to any one of claims 1 to 3, wherein the component (A) is polypropylene.
5. The flame-retardant resin composition according to any one of claims 1 to 4, wherein the component (C) contains a halogen-based flame retardant.
6. The flame-retardant resin composition according to any one of claims 1 to 5, wherein the component (C) contains a bromine-based flame retardant.
7. The flame-retardant resin composition according to any one of claims 1 to 6, wherein the component (C) comprises tris (tribromoneopentyl) phosphate.
8. The flame-retardant resin composition according to any one of claims 1 to 7, wherein the component (C) has a melting point of 50 ℃ or higher and 250 ℃ or lower.
9. The flame-retardant resin composition according to any one of claims 1 to 8, wherein the decomposition temperature of the component (C) is 200 ℃ or higher and 400 ℃ or lower.
10. The flame-retardant resin composition according to any one of claims 1 to 9, wherein the component (B) has a 2, 3-dimethyl-2, 3-diphenyl-butane structure.
11. The flame-retardant resin composition according to any one of claims 1 to 10, wherein the component (B) is 2, 3-dimethyl-2, 3-diphenyl-butane or poly-1, 4-diisopropylbenzene.
12. A molded article produced using the flame-retardant resin composition described in any one of 1 to 11.
According to the present invention, a flame-retardant resin composition and a molded article can be provided, which can suppress the content of antimony and can provide a molded article having excellent flame retardancy.
Detailed Description
In the present specification, "x to y" mean "x or more and y or less".
In the present specification, the preferable ones can be optionally used, and the combination of the preferable ones can be said to be more preferable.
Any constituent element may be added within a range not impairing the effects of the invention.
In the present specification, "atomic number XX to YY" in the expression "substituted or unsubstituted ZZ group having atomic numbers XX to YY" represents the atomic number when the ZZ group is unsubstituted, and does not include the atomic number of the substituent when the substitution occurs. Here, "YY" is larger than "XX", "XX" and "YY" each represent an integer of 1 or more.
The "unsubstituted" when it is said to be "substituted or unsubstituted" means that a hydrogen atom is bonded without being substituted by the above-mentioned substituent.
In one embodiment of the flame-retardant resin composition of the present invention, the following components (A) to (C) are contained at the following contents, the melt flow rate at 190 ℃ is 0.05g/10 min or more and 12g/10 min or less, and antimony is substantially not contained.
(A) The polyolefin (hereinafter also referred to as the "component (A)") is 65 to 98.9 mass% (preferably 70 to 95.7 mass%, more preferably 75 to 94.65 mass%, still more preferably 80 to 93.6 mass%, particularly preferably 85 to 91.55 mass%)
(B) The radical generator (hereinafter also referred to as the "(B) component") is 0.1 to 5% by mass (preferably 0.30 to 4% by mass, more preferably 0.35 to 3% by mass, still more preferably 0.40 to 2% by mass, particularly preferably 0.45 to 1% by mass)
(C) 1 to 30 mass% (preferably 4 to 26 mass%, more preferably 5 to 22 mass%, further preferably 6 to 18 mass%, particularly preferably 8 to 14 mass%) of a flame retardant (hereinafter also referred to as "component (C)")
This makes it possible to obtain a molded article having excellent flame retardancy while suppressing the content of antimony.
In one embodiment of the flame-retardant resin composition of the present invention, the Melt Flow Rate (MFR) at 190 ℃ is 0.05 to 12g/10 min, preferably 0.1 to 11g/10 min, more preferably 0.3 to 10g/10 min, still more preferably 0.5 to 9g/10 min, and particularly preferably 0.8 to 8g/10 min.
In one embodiment of the flame-retardant resin composition of the present invention, MFR is measured at 190 ℃ under 2.16kg in accordance with ASTM D-1238 (2013).
In one embodiment of the flame-retardant resin composition of the present invention, antimony is substantially not contained.
"substantially no antimony is contained" means that the content is less than the detection limit (2000ppm) of the following measurement apparatus.
The antimony content was measured using an EDS (energy dispersive X-ray analysis) apparatus built in JSM-6390LA (manufactured by Nippon electronics Co., Ltd.).
The polyolefin is not particularly limited, but examples thereof include homopolyolefins, olefin copolymers, and the like.
Examples of the polyolefin include polypropylene and polyethylene. From the viewpoint of heat resistance of the molded article, polypropylene is preferred.
Examples of the olefin include ethylene, propylene, butene, hexene, and α -olefin.
Examples of the α -olefin include 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
Examples of the homopolyolefin include homopolyethylene (for example, low density polyethylene, linear low density polyethylene, and high density polyethylene), homopolypropylene, and the like. From the viewpoint of heat resistance of the molded article, homopolypropylene is preferable.
The olefin copolymer may be a block copolymer, a random copolymer or a mixture thereof.
Examples of the olefin copolymer include a propylene copolymer and an ethylene copolymer. Examples of the propylene copolymer include copolymers of propylene and the above-mentioned olefins other than propylene. Examples of the ethylene copolymer include copolymers of ethylene and the above-mentioned olefins other than ethylene. The number of the olefins may be 1 alone or 2 or more in combination.
The MFR of the component (A) at 230 ℃ is preferably 0.01 to 100g/10 min, more preferably 0.1 to 90g/10 min, still more preferably 1 to 70g/10 min, particularly preferably 3 to 50g/10 min, from the viewpoints of lightweight, moldability, rigidity of molded articles, and impact resistance of molded articles.
From the viewpoint of moldability, the content of the thermoplastic resin composition may be 0.1g/10 min or more and less than 15g/10 min, 15 to 50g/10 min or the like.
The MFR of component (A) at 230 ℃ was measured under the conditions of 230 ℃ and 2.16kg in accordance with ASTM D-1238 (2013).
Examples of commercially available polyolefins include polypropylene "Prime Polypro", "Poly-Fine" and "Prime TPO" manufactured by Prime Polymer corporation (for example, models "J-700 GP", "J106 MG", "J707G", "H700", "H-100M", "J105P", "J707P", "F-300 SP", "J-466 HP" and "E-105 GM"); polypropylene available from shinning corporation (for example, model "J-966 HP"); various polyethylene resins available from Prime Polymer Ltd, such as "HI-ZEX", "NEO-ZEX", "ULT-ZEX", "モアテシク" and "Evolu" (for example, high-density polyethylene resin, type "2200J"); low-density polyethylene (for example, model "Petrothene 190") available from Tosoh corporation, and the like.
The component (a) is preferably polypropylene from the viewpoint of heat resistance of the molded article.
(A) The component (A) may be 1 kind alone or 2 or more kinds in combination.
The decomposition temperature of the component (B) is preferably 80 to 280 ℃ and more preferably 120 to 240 ℃ from the viewpoint of flame retardancy.
(B) The decomposition temperature of the component (c) is measured by TGA (thermogravimetric analysis)/DSC (differential scanning calorimeter) 1 described later.
The melting point of the component (B) is preferably 50 to 250 ℃ and more preferably 100 to 200 ℃ from the viewpoint of flame retardancy.
(B) The melting point of the component (A) was measured by TGA/DSC1 described later.
Examples of the component (B) include organic peroxides, initiators for breaking carbon-carbon bonds, initiators for breaking nitrogen-nitrogen bonds, and the like.
(B) Ingredient (b) preferably comprises a 2, 3-dimethyl-2, 3-diphenyl-butane structure (also known as a diisopropylbenzene structure).
Examples of the component (B) include 2, 3-dimethyl-2, 3-diphenyl-butane and poly-1, 4-diisopropylbenzene (tri-1, 4-diisopropylbenzene).
The component (B) is preferably 2, 3-dimethyl-2, 3-diphenyl-butane from the viewpoint of flame retardancy.
In addition, the component (B) is preferably poly-1, 4-diisopropylbenzene from the viewpoint of flame retardancy.
The melting point of the component (C) is preferably 50 to 250 ℃ and more preferably 100 to 200 ℃ from the viewpoint of flame retardancy.
(C) The melting point of the component (A) was measured by TGA/DSC1 described later.
The decomposition temperature of the component (C) is preferably 200 to 400 ℃ and more preferably 250 to 350 ℃ from the viewpoint of heat resistance.
(C) The decomposition temperature of the component (A) was measured by TGA/DSC1 described later.
Examples of the component (C) include halogen flame retardants and phosphorus flame retardants.
Examples of the halogen-based flame retardant include 2, 4, 6-tris (2, 4, 6-tribromophenoxy) -1, 3, 5-triazine, brominated epoxy oligomer, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), decabromodiphenyl ether, tetrabromobisphenol a, halogenated polycarbonate (co) polymer, halogenated polycarbonate or oligomer of halogenated polycarbonate (co) polymer, halogenated polystyrene, halogenated polyolefin, and the like.
Examples of the halogen flame retardant include bromine flame retardants and the like.
The component (C) preferably contains a bromine-based flame retardant from the viewpoint of flame retardancy.
Examples of the bromine-based flame retardant include 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromopropyloxy) phenyl ] propane, bis [3, 5-dibromo-4- (2, 3-dibromopropyloxy) phenyl ] sulfone, pentabromobenzyl acrylate polymer, 1, 2, 5, 6, 9, 10-hexabromocyclododecane, 2, 4, 6-tris- (2, 4, 6-tribromophenoxy) -1, 3, 5-triazine, 2-bis (bromomethyl) -1, 3-propanediol, tribromo-neopentyl alcohol, 2-bis (4-allyloxy-3, 5-dibromophenyl) propane, BC-52-tetrabromobisphenol A, BC-58 tetrabromobisphenol A, tetrabromobisphenol A, 1, 1 '- [ ethylenebis (oxy) ] bis (2, 4, 6-tribromobenzene), pentabromobenzyl acrylate, tribromophenol acrylate, octabromodiphenyl ether, 2' - [ isopropylidenebis [ (2, 6-dibromo-4, 1-phenylene) oxy ] ] diethanol, N-methyl hexabromodiphenylamine, TBA bisbromoethyl ether, tris (tribromoneopentyl) phosphate, tris (dibromopropyl) isocyanurate, and the like.
(C) Component (c) preferably contains tris (tribromoneopentyl) phosphate and tris (dibromopropyl) isocyanurate, and more preferably contains tris (tribromoneopentyl) phosphate from the viewpoint of flame retardancy.
(C) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In one embodiment of the flame retardant resin composition of the present invention, an additive may be further contained, if necessary.
Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial or antifungal agents, pigments, natural inorganic fillers, and the like.
The ultraviolet absorber is not particularly limited, but examples thereof include benzophenone compounds, benzotriazole compounds, benzoate compounds, polyamide polyether block copolymers (for imparting permanent antistatic properties), and the like.
The antioxidant is not particularly limited, but examples thereof include a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant.
The lubricant is not particularly limited, but examples thereof include fatty acid amide-based lubricants, fatty acid ester-based lubricants, fatty acid-based lubricants, and fatty acid metal salt-based lubricants.
The crystal nucleating agent is not particularly limited, but examples thereof include sorbitol, phosphorus nucleating agents, rosins, petroleum resins, and the like.
The softener is not particularly limited, but examples thereof include a fluid paraffin, a mineral oil softener (processing oil) for non-aromatic rubber, and the like.
The antistatic agent is not particularly limited, but examples thereof include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, fatty acid partial esters such as glycerin fatty acid monoesters, and the like.
The metal deactivator is not particularly limited, but examples thereof include a hydrazine-based metal deactivator, a nitrogen compound-based metal deactivator, and a phosphite-based metal deactivator.
The antibacterial or antifungal agent is not particularly limited, but examples thereof include organic compounds, natural organic antibacterial or antifungal agents, and inorganic antibacterial or antifungal agents.
The pigment is not particularly limited, but examples thereof include inorganic pigments and organic pigments.
Examples of the inorganic pigment include titanium oxide, calcium carbonate, and carbon black.
Examples of the organic pigment include azo pigments, acid dye lakes (レ - キ), basic dye lakes, and condensed polycyclic pigments.
When a natural inorganic filler is contained, the content of the natural inorganic filler is preferably 10% by mass or less, and more preferably 0 to 10% by mass, based on 100% by mass of the flame-retardant resin composition.
Examples of the natural inorganic filler include talc and wollastonite.
The natural inorganic filler preferably contains 1 or more selected from talc and wollastonite from the viewpoint of flame retardancy.
The average particle diameter (D50) of the natural inorganic filler in the case of talc is preferably 7 to 30 μm, more preferably 10 to 20 μm, from the viewpoint of improving the flame retardancy of the flame-retardant resin composition.
The average particle diameter (D50) is a diameter at which the large particle diameter side and the small particle diameter side are equal when the powder is divided into 2 parts from a certain particle diameter.
When the natural inorganic filler is talc, the average particle diameter (D50) of the natural inorganic filler is measured by a laser diffraction particle size distribution measuring apparatus.
When the natural inorganic filler is wollastonite, the 400 mesh (ASTM standard) pass rate is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more, from the viewpoint of improving the flame retardancy of the resin composition. Further, it is preferably 100% or less.
The 400 mesh passage rate was determined by the passage rate when a sample was placed on a 400 mesh net and vibrated by a vibrating screen.
The water content in the case where the natural inorganic filler is talc is preferably 0 to 0.5%, more preferably 0 to 0.1%, from the viewpoint of blending (mixing) and from the viewpoint of suppressing a defect during molding.
The moisture of natural inorganic fillers was determined using the karl fischer method.
The whiteness W value of talc as the natural inorganic filler is preferably 50 to 100%, more preferably 70 to 100%, from the viewpoint of appearance of the molded article.
The whiteness W value of the natural inorganic filler was measured using an SM color computer.
The apparent specific gravity when the natural inorganic filler is talc is preferably 0.2 to 0.8g/ml, more preferably 0.3 to 0.5g/ml, from the viewpoint of feeding at the time of compounding.
The apparent specific gravity of the natural inorganic filler is measured in accordance with JIS K5101.
The 500 ℃ heat loss at 500 ℃ when the natural inorganic filler is talc is preferably 0 to 6%, more preferably 0 to 3%, from the viewpoint of the appearance of the molded article.
The 500 ℃ heat loss at 500 ℃ when the natural inorganic filler is talc is measured using a muffle furnace.
In addition, as the additive, the following may be added within a range not impairing the effects of the invention:
nitrogen-based compound, metal hydroxide, silicone-based flame retardant, organic alkali metal salt, organic alkaline earth metal salt,
Boric acid compounds such as zinc borate, zinc metaborate, barium metaborate, aluminum borate and sodium polyborate, and the like,
Silicon compounds such as silicon dioxide (silica), synthetic amorphous silicon oxide (silica), aluminum silicate, magnesium silicate, calcium silicate, zirconium silicate and diatomaceous earth, and the like,
Metal oxides such as aluminum oxide, magnesium oxide, barium oxide, titanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, zirconium-antimony composite oxide, and
expandable graphite, and the like.
The above additives may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The amount of the additive is not particularly limited as long as the properties of the flame-retardant resin composition are not impaired.
One embodiment of the flame-retardant resin composition of the present invention is essentially composed of components (a) to (C) and optional additives, and may further contain inevitable impurities within a range not impairing the effects of the present invention.
In one embodiment of the flame-retardant resin composition of the present invention, for example, 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, 98 to 100 mass%, or 100 mass% may be composed of:
(A) component (C) to component (C), or
(A) Components (A) to (C) and optional additives.
One embodiment of the flame-retardant resin composition of the present invention can be produced, for example, by blending the components (A) to (C) and, if necessary, additives and hot-melt mixing (kneading). The above components can be blended and kneaded by, for example, a henschel mixer, a banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a kneader, or the like. The heating temperature during kneading is usually 160 to 250 ℃.
The components may be mixed and premixed by a commonly used apparatus (for example, a ribbon mixer, a tumbler, or the like), and then kneaded by the above apparatus.
The shape of one embodiment of the flame-retardant resin composition of the present invention includes particles.
One embodiment of the molded article of the present invention can be produced using the above-described flame-retardant resin composition.
The production can be carried out by, for example, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like.
One embodiment of the molded article of the present invention can be suitably used for, for example, automobiles, industrial materials, building materials, electronic and electrical equipment, OA equipment, mechanical fields, home appliances, and home appliances (high-grade home appliances).
Examples
Examples 1 to 9 and comparative examples 1 to 2
[ production of flame-retardant resin composition ]
Each of the components shown in Table 1 was melt-mixed at a compounding ratio (mass%) shown in Table 1 by a twin-screw extruder TEM-30 (manufactured by Nippon Steel Co., Ltd.) at 200 ℃ and 300rpm to prepare pellets (flame-retardant resin composition).
The ingredients used are shown below.
(A) Composition (I)
In table 1, the parenthesized values of the resins a to D are the following Melt Flow Rates (MFR).
Resin A: h-700 (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C.: 10g/10 min)
Resin B: H-100M (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C.: 1.5g/10 min)
Resin C: f-300SP (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C.: 3.1g/10 min)
Resin D: j-700GP (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C: 8.0g/10 min)
Resin E: J105P (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C: 15g/10 min)
Resin G: J707P (ethylene-propylene block copolymer, manufactured by Prime Polymer, Ltd., MFR at 230: 27g/10 min)
Resin H: e-105GM (homopolypropylene, manufactured by Prime Polymer, Ltd., MFR at 230 ℃ C: 0.5g/10 min)
(B) Composition (I)
Radical generator a: CC-P3 (Poly-1, 4-diisopropylbenzene, manufactured by United Initiators, a compound represented by the following formula, melting point: 105-135 ℃ C., decomposition temperature: 220 ℃ C.)
[ solution 1]
Radical generator B: NOFMER BC-90 (2, 3-dimethyl-2, 3-diphenyl-butane, manufactured by Nichikoku corporation, purity: 86%, melting point: 80-130 ℃ C., decomposition temperature: 140 ℃ (TGA (thermogravimetric analysis) 1% weight loss) compound represented by the following formula)
[ solution 2]
(C) Composition (I)
Flame retardant A: CR-900 (Tribromoneopentyl phosphate, manufactured by Daba chemical Co., Ltd., melting point: 182 ℃ C., decomposition temperature: 313 ℃ (TGA 1% weight loss))
(A) The MFR of the component (B) was measured at 230 ℃ under 2.16kg in accordance with ASTM D-1238 (2013).
(B) The melting points of component (A) and component (C) were measured by TGA/DSC1 (manufactured by METTLER TOLEDO Co.). Heating from 30 ℃ to 600 ℃, and heating at the speed of 20 ℃/min and N2And (4) measuring under an atmosphere condition.
(B) The decomposition temperatures of component (A) and component (C) were measured by TGA/DSC 1. Heating from 30 ℃ to 600 ℃, and heating at the speed of 20 ℃/min and N2The temperature at which 1% by weight reduction was achieved was taken as the decomposition temperature in the atmospheric measurement.
[ measurement of MFR of flame-retardant resin composition ]
The MFR of the resulting pellets was measured at 190 ℃ under 2.16kg in accordance with ASTM D-1238 (2013).
The results are shown in Table 1.
[ production of molded article ]
The obtained pellets were dried at 80 ℃ and then molded at 200 ℃ by an injection molding machine ("NEX 110 III" manufactured by Nichisu resin industries Co., Ltd.) to produce UL test pieces (test pieces for UL94 test described below) (molded articles) having a thickness of 0.8mm, 1.6mm or 3.2mm, respectively.
[ measurement of antimony (Sb) content ]
The obtained particles and molded bodies were measured with an acceleration voltage of 20kV using an EDS (energy dispersive X-ray analysis) apparatus built in JSM-6390LA (manufactured by Nippon electronics Co., Ltd.). The results are shown in Table 1. "-" indicates below the detection limit (2000 ppm).
[ flame retardancy evaluation 1 (thickness: 0.8mm) ]
A UL test piece having a thickness of 0.8mm obtained in the production of a molded article was subjected to a vertical burning test (UL94 test) in accordance with UL94 standard using a flame retardancy evaluation tester (HVUL plastic UL burning test chamber, manufactured by Atlas). Specifically, 5 test pieces were given flame retardancy ratings according to UL94 standards based on the respective first and second burning times, whether cotton was on fire, and the like.
The results are shown in Table 1.
[ flame retardancy evaluation 2 (thickness 1.6mm) ]
Evaluation was performed in the same manner as in flame retardancy evaluation 1 except that a UL test piece having a thickness of 1.6mm obtained in the production of a molded article was used instead of the UL test piece having a thickness of 0.8 mm. The results are shown in Table 1.
[ flame retardancy evaluation 3 (thickness: 3.2mm) ]
Evaluation was performed in the same manner as in flame retardancy evaluation 1 except that a UL test piece having a thickness of 3.2mm obtained in the production of a molded article was used instead of the UL test piece having a thickness of 0.8 mm. The results are shown in Table 1.
[ Table 1]
While several embodiments and/or examples of the present invention have been described in detail above, those skilled in the art can easily make various modifications to these illustrated embodiments and/or examples without substantially departing from the novel teachings and effects of the present invention. Therefore, these various modifications are also included in the scope of the present invention.
The contents of the documents described in the present specification and the priority basic application based on the paris convention of the present application are incorporated in their entirety into the present specification.
Claims (12)
1. A flame-retardant resin composition which contains substantially no antimony and contains the following components A to C in the following amounts,
the flame-retardant resin composition has a melt flow rate of 0.05g/10 min to 12g/10 min at 190 ℃,
component A: a polyolefin in an amount of 65 to 98.9 mass%,
and B component: 0.1 to 5% by mass of a radical generator,
and C, component C: the flame retardant is 1 to 30 mass%.
2. The flame-retardant resin composition according to claim 1,
the component A has a melt flow rate of 0.1g/10 min or more and less than 15g/10 min at 230 ℃.
3. The flame-retardant resin composition according to claim 1 or 2,
the component A comprises polypropylene.
4. The flame-retardant resin composition according to any one of claims 1 to 3, wherein,
the component A is polypropylene.
5. The flame-retardant resin composition according to any one of claims 1 to 4,
the component C contains a halogen-based flame retardant.
6. The flame-retardant resin composition according to any one of claims 1 to 5,
the component C contains a bromine-based flame retardant.
7. The flame-retardant resin composition according to any one of claims 1 to 6,
the C component contains tris (tribromoneopentyl) phosphate.
8. The flame-retardant resin composition according to any one of claims 1 to 7,
the melting point of the component C is 50 ℃ to 250 ℃.
9. The flame-retardant resin composition according to any one of claims 1 to 8,
the decomposition temperature of the component C is 200 ℃ to 400 ℃.
10. The flame-retardant resin composition according to any one of claims 1 to 9,
the component B comprises a 2, 3-dimethyl-2, 3-diphenyl-butane structure.
11. The flame-retardant resin composition according to any one of claims 1 to 10,
the component B is 2, 3-dimethyl-2, 3-diphenyl-butane or poly (1, 4-diisopropylbenzene).
12. A molded article produced by using the flame-retardant resin composition according to any one of claims 1 to 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018183410 | 2018-09-28 | ||
| JP2018-183410 | 2018-09-28 | ||
| PCT/JP2019/037694 WO2020067207A1 (en) | 2018-09-28 | 2019-09-25 | Flame-retardant resin composition and molded body |
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| CN112739765A true CN112739765A (en) | 2021-04-30 |
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| Country | Link |
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| JP (1) | JP7536646B2 (en) |
| CN (1) | CN112739765A (en) |
| WO (1) | WO2020067207A1 (en) |
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| US3850882A (en) * | 1971-12-01 | 1974-11-26 | Phillips Petroleum Co | Flame retarded compositions and additive systems therefor |
| EP1239005A1 (en) * | 2001-02-27 | 2002-09-11 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| US20060047049A1 (en) * | 2004-09-01 | 2006-03-02 | Hideaki Onishi | Flame retardant compositions for flammable plastics and flame retarded plastic compositions containing the same |
| US20110152412A1 (en) * | 2008-08-29 | 2011-06-23 | Akzo Nobel N.V. | Flame retardant polyolefin composition |
| CN103827197A (en) * | 2011-12-06 | 2014-05-28 | 株式会社艾迪科 | Flame retardant polyolefin resin composition |
| CN107406659A (en) * | 2015-03-24 | 2017-11-28 | 株式会社自动网络技术研究所 | Wire covering materials composition, insulated electric conductor and wire harness |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03179058A (en) * | 1989-12-07 | 1991-08-05 | Nippon Petrochem Co Ltd | Flame-retardant resin composition |
| EP2318455A1 (en) * | 2008-08-29 | 2011-05-11 | Akzo Nobel N.V. | Flame retardant polyolefin composition |
| US20150284535A1 (en) * | 2012-03-16 | 2015-10-08 | Basf Se | Nor-hals compounds as flame retardants |
| EP3574044B1 (en) * | 2017-01-24 | 2022-03-09 | THOR GmbH | Flame-retardant compositions with improved effect, comprising a phosphonic acid derivative |
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2019
- 2019-09-25 WO PCT/JP2019/037694 patent/WO2020067207A1/en active Application Filing
- 2019-09-25 CN CN201980062108.4A patent/CN112739765A/en active Pending
- 2019-09-25 JP JP2020549312A patent/JP7536646B2/en active Active
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|---|---|---|---|---|
| US3850882A (en) * | 1971-12-01 | 1974-11-26 | Phillips Petroleum Co | Flame retarded compositions and additive systems therefor |
| EP1239005A1 (en) * | 2001-02-27 | 2002-09-11 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| US20060047049A1 (en) * | 2004-09-01 | 2006-03-02 | Hideaki Onishi | Flame retardant compositions for flammable plastics and flame retarded plastic compositions containing the same |
| CN1743369A (en) * | 2004-09-01 | 2006-03-08 | 第一Fr株式会社 | Flame retardant compositions for flammable plastics and flame retarded plastic compositions containing the same |
| US20110152412A1 (en) * | 2008-08-29 | 2011-06-23 | Akzo Nobel N.V. | Flame retardant polyolefin composition |
| CN103827197A (en) * | 2011-12-06 | 2014-05-28 | 株式会社艾迪科 | Flame retardant polyolefin resin composition |
| CN107406659A (en) * | 2015-03-24 | 2017-11-28 | 株式会社自动网络技术研究所 | Wire covering materials composition, insulated electric conductor and wire harness |
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| Publication number | Publication date |
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| WO2020067207A1 (en) | 2020-04-02 |
| JP7536646B2 (en) | 2024-08-20 |
| JPWO2020067207A1 (en) | 2021-08-30 |
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