WO2011007687A1 - 難燃性熱可塑性樹脂組成物および成形品 - Google Patents
難燃性熱可塑性樹脂組成物および成形品 Download PDFInfo
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- WO2011007687A1 WO2011007687A1 PCT/JP2010/061368 JP2010061368W WO2011007687A1 WO 2011007687 A1 WO2011007687 A1 WO 2011007687A1 JP 2010061368 W JP2010061368 W JP 2010061368W WO 2011007687 A1 WO2011007687 A1 WO 2011007687A1
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- compound
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- weight
- thermoplastic resin
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- 0 C*c(cccc1)c1O Chemical compound C*c(cccc1)c1O 0.000 description 3
Classifications
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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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
- C08K5/16—Nitrogen-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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Definitions
- the present invention relates to a flame retardant thermoplastic resin composition, and in particular, a flame retardant thermoplastic resin having significantly improved corrosiveness to metals by containing a phosphinate and a compound having a specific structure in the thermoplastic resin. Relates to the composition.
- Polyester resins and polyamide resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of their excellent properties such as injection moldability and mechanical properties. Further, since polyester resins and polyamide resins are crystalline plastics having a high melting point, an extruder and an injection molding machine for melt kneading are required to have a high processing temperature.
- Polyester resins and polyamide resins are inherently flammable, so they have a balance of general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical / electronic parts, and automotive parts. In addition to this, safety against flame, that is, flame retardancy, is required, and high flame retardancy showing V-0 of UL-94 standard is often required.
- a method of imparting flame retardancy to a polyester resin or polyamide resin a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is generally used. There is a movement to worry about the environmental impact of halogenated organic compounds.
- Patent Document 1 and Patent Document 2 disclose that a phosphinate and a nitrogen-containing compound are blended as non-halogen flame retardants, but the flame retardants are flame-retardant.
- the polyester resin and the polyamide resin have a problem that the screw of the kneading apparatus is corroded or the injection mold is corroded by the corrosive gas generated from the flame retardant.
- Patent Document 1 and Patent Document 2 cannot solve the above-described problems, and the solution is essential. Therefore, there has been a long-awaited development of a new technology that can solve the above-described problems and can satisfy the demands of recent mechanical mechanism parts, electrical / electronic parts, and automobile parts.
- the object of the present invention is to obtain a flame retardant thermoplastic resin composition having a significantly improved corrosiveness to metals while maintaining a high degree of flame retardancy. Furthermore, the corrosiveness to metals is greatly improved. It is an object of the present invention to provide a molded product useful as a mechanical mechanism part, an electric / electronic part, or an automobile part.
- the present inventors have solved the above-mentioned problems by containing (B) phosphinic acid salts and (C) a specific amount of a compound having a specific structure. I found what I could do and reached the present invention. That is, the present invention for solving such a problem is characterized by the following configuration.
- thermoplastic resin (A) 65 to 99% by weight of a thermoplastic resin, (B) at least one phosphinic acid salt selected from phosphinic acid salts, diphosphinic acid salts, phosphinic acid polymers, or diphosphinic acid polymers 1
- phosphinic acid salt selected from phosphinic acid salts, diphosphinic acid salts, phosphinic acid polymers, or diphosphinic acid polymers 1
- a flame-retardant thermoplastic resin composition comprising -35 wt% and (C) 0.001-0.70 wt% of a compound having a structure represented by the following formula (1).
- thermoplastic resin (A) is at least one selected from polyester resins, polyamide resins, and polycarbonate resins.
- the compound (C) is a compound represented by the following formula (2).
- thermoplastic resin composition and molded article according to any one of (1) to (4), which have a property of not corroding a metal in a heat treatment at a heat treatment temperature of 270 ° C. and a heat treatment time of 3 hours.
- the phosphoric acid ester compound (D) is contained in an amount of 0.001 to 1.0 part by weight with respect to 100 parts by weight of (A), (B) and (C).
- the flame-retardant thermoplastic resin composition according to any one of the above.
- the flame-retardant thermoplastic resin composition of the present invention is greatly improved in corrosiveness to metals while maintaining high flame retardancy.
- the molded product made of the flame-retardant thermoplastic resin composition of the present invention is useful as a molded product for mechanical mechanism parts, electrical / electronic parts, automobile parts and the like.
- the present invention is a flame-retardant thermoplastic resin composition containing 65-99% by weight of (A) a thermoplastic resin.
- the thermoplastic resin (A) in the present invention is a polyolefin resin (low density polyethylene resin, high density polyethylene resin, polypropylene resin), polyester resin, polyamide resin, aliphatic polyester resin such as polylactic acid, polystyrene resin, polyacetal resin.
- Acrylic resins such as aromatic and aliphatic polyketone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, polymethyl methacrylate resins, styrene resins (polystyrene resins, acrylonitrile / styrene resins (AS Resin), acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / ethylene / styrene resin (AES resin), acrylonitrile / acrylic / styrene resin (AAS resin), salt Polyethylene / acrylonitrile / styrene resin (ACS resin)), polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, methyl methacrylate / styrene (MS resin), polycarbonate resin, polyarylate resin, polysulfone resin, polyether
- thermoplastic resin (A) polyester resins, polyamide resins, and alloy resins thereof are preferably used because of their excellent crystallinity.
- the blending amount of the (A) thermoplastic resin used in the present invention is 65 to 99% by weight, preferably 70 to 95% by weight, and more preferably 75 to 90% by weight. Sufficient moldability is obtained at 65 wt% or more, and good mechanical properties are obtained at 99 wt% or less.
- the polyester resin which is a preferred component (A) in the present invention is (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, (c) It is a polymer or copolymer having at least one selected from lactones as a main structural unit.
- dicarboxylic acid or ester-forming derivatives thereof examples include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon
- Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid
- diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Fragrances such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol, or long chain glycols having a molecular weight of 200 to 100,000, ie, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. family dioxy compound i.e., 4,4'-dihydroxybiphenyl, hydroquinone, t- butyl hydroquinone, bisphenol A, bisphenol S, bisphenol F and this Such ester forming derivatives.
- aliphatic glycols having 2 to 20 carbon atoms that is,
- Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate.
- Aromatic polyester resin polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate , Polypropylene sebake DOO, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.
- hydroxycarboxylic acid examples include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these
- the polymer or copolymer having these as a structural unit examples include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / ⁇ -hydroxybutyric acid / ⁇ -hydroxyyoshide. Aliphatic polyester resins such as herbic acid can be mentioned.
- polylactic acid it is also possible to use polylactic acid having a stereocomplex structure composed of poly-L-lactic acid units and poly-D-lactic acid units.
- lactone examples include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like.
- polycaprolactone is used as a polymer or copolymer having these as structural units.
- a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol.
- a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, and an aliphatic diol selected from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, propylene glycol, or butanediol or an ester-forming property thereof.
- a polymer or copolymer having a derivative as a main structural unit is more preferred.
- polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, and the combination of polyethylene naphthalate and polybutylene terephthalate / polytetramethylene glycol have improved mechanical properties such as tensile elongation. Therefore, the combination of polybutylene terephthalate and polybutylene terephthalate / polytetramethylene glycol is particularly preferably used because of its excellent injection moldability. Further, polybutylene terephthalate / polytetramethylene glycol is commercially available under the name "Hytrel" (TM) from Du Pont-Toray Corporation.
- TM Hytrel
- the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.
- a liquid crystalline polyester that can form anisotropy when melted may be used as the polyester resin.
- the structural unit of the liquid crystalline polyester include an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, and an aromatic iminooxy unit.
- the amount of carboxyl end groups of the polyester resin is preferably 50 eq / t or less, more preferably 30 eq / t or less, in terms of fluidity, hydrolysis resistance and heat resistance, and 20 eq / t It is more preferably t or less, and particularly preferably 10 eq / t or less.
- the lower limit is 0 eq / t.
- the carboxyl end group amount of the polyester resin is a value measured by dissolving in an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.
- the amount of hydroxyl terminal groups of the polyester resin is preferably 50 eq / t or more, more preferably 80 eq / t or more, and 100 eq / t or more in terms of moldability and fluidity. Is more preferable, and particularly preferably 120 eq / t or more. The upper limit is 180 eq / t.
- the viscosity of the polyester resin is preferably in the range of 0.36 to 1.60 dl / g in terms of moldability when the o-chlorophenol solution is measured at 25 ° C. More preferably, it is in the range of 50 to 1.50 dl / g.
- the molecular weight of the (A) component polyester resin used in the present invention is preferably in the range of more than 8,000 and less than 500,000 in weight average molecular weight (Mw) in terms of heat resistance, and more than 8,000 and less than 300,000. Is more preferable, and more preferably in the range of more than 8000 and 250,000 or less.
- Mw of the polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
- Examples of the method for producing a polyester resin in the present invention include known polycondensation methods and ring-opening polymerization methods, and any of batch polymerization and continuous polymerization may be used. In addition, any of transesterification and direct polymerization reactions can be applied. However, the amount of carboxyl end groups can be reduced, and the effect of improving hydrolysis resistance and fluidity can be increased. Polymerization is preferred, and direct polymerization is preferred in terms of cost.
- the polyester resin is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof
- the ester-forming derivative and the diol or the ester-forming derivative thereof can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction.
- the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexylditin oxide, Didodecyltin oxide, Triethyltin hydroxide, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, di
- organic titanium compounds and tin compounds are preferred, Further, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferable, and titanic acid Tetra -n- butyl ester is particularly preferred.
- These polymerization reaction catalysts may be used alone or in combination of two or more.
- the addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight, and 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polyester resin in terms of mechanical properties, moldability and color tone. A range of parts is more preferred.
- the preferred polyamide resin as the component (A) is a polyamide mainly composed of amino acid, lactam or diamine and dicarboxylic acid.
- Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ⁇ -caprolactam and ⁇ -laurolactam, and pentamethylenediamine.
- a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength.
- Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polytetramethylene adipamide (nylon 46), polypentamethylene adipamide (nylon 56), polytetramethylene sebacamide (nylon 410), polypentamethylene sebacamide (nylon 510), poly Hexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6) / 66), polycaproamide / Po Hexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copoly
- the Particularly preferable polyamide resins nylon 6, nylon 66, nylon 12, nylon 610, nylon 6/66 copolymer, and nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 12, and nylon 6T / 6 copolymers, etc. It is also practically preferable to use these polyamide resins as a mixture depending on the required properties such as impact resistance and molding processability.
- the degree of polymerization of these polyamide resins is preferably in the range of 1.5 to 7.0 as a relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml, and particularly 2.0.
- a polyamide resin in the range of ⁇ 6.0 is preferred.
- thermoplastic resin contains 50 to 99% by weight of the polyester resin and 50 to 1% by weight of the polycarbonate resin in that the tensile properties are greatly improved. It is preferable. 60 to 90% by weight of polyester resin and 20 to 2% by weight of polycarbonate resin are more preferable, 70 to 80% by weight of polyester resin and 10 to 3% by weight of polycarbonate resin are more preferable, 70 to 80% by weight of polyester resin and 7 to 7% of polycarbonate resin are preferable. 3% by weight is particularly preferred.
- the flame-retardant thermoplastic resin composition of the present invention comprises (B) at least one phosphinic acid salt selected from phosphinic acid salts, diphosphinic acid salts, phosphinic acid polymers, or diphosphinic acid polymers. Contains 35% by weight.
- the phosphinic acid salt in the present invention is a compound represented by the following formula (4).
- R1 and R2 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms or an aryl group, and may be linear or branched. , Aluminum or zinc, and n is an integer of 1 to 4.
- the diphosphinic acid salt in the present invention is a compound represented by the following formula (5).
- R1 ′ and R2 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms or an aryl group, and may be linear or branched. Is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group or an arylalkylene group, and M ′ is calcium, aluminum or zinc. N ′ is an integer of 1 to 4.)
- the phosphinates the above-mentioned phosphinate polymers or diphosphinate polymers can be used.
- Aluminum is preferable as the metal component in terms of excellent mechanical properties, corrosiveness to metals, melt residence stability, fluidity, flame retardancy, and specifically, aluminum ethylmethylphosphinate or aluminum diethylphosphinate Are preferred, and aluminum diethylphosphinate is more preferred.
- Examples of commercially available phosphinic acid salts include “Exolit” (registered trademark) OP1230 and OP1240 manufactured by Clariant Japan.
- a mixture containing the component (B), a nitrogen-containing compound and / or a boron-containing compound is also commercially available.
- Examples of commercially available products include OP1312, and any of them can be preferably used.
- the content of at least one phosphinate selected from (B) a phosphinate, a diphosphinate, a phosphinate polymer, or a diphosphinate polymer is 1 to 35% by weight. It is preferably 3 to 30% by weight, and more preferably 5 to 25% by weight. A flame retardant effect is obtained at 1% by weight or more, and good mechanical properties are obtained at 35% by weight or less.
- the flame-retardant thermoplastic resin composition of the present invention contains 0.001 to 0.70% by weight of a compound (C) having a structure represented by the following formula (1).
- (C) the compound having the structure represented by the formula (1) is A compound represented by the following formula (2) is preferable.
- X represents a heterocyclic group having a nitrogen atom
- X may be any heterocyclic group as long as it is a heterocyclic group having a nitrogen atom.
- X may be an atom selected from a carbon atom, an oxygen atom, or a sulfur atom. It has seeds or two or more.
- the number of atoms constituting the ring is preferably 3 to 14 in terms of excellent mechanical properties, corrosiveness to metals, melt residence stability, fluidity, flame retardancy, etc., and preferably 5 to 7 More preferably.
- any of a saturated ring, a partially unsaturated ring, and an aromatic ring group may be sufficient, and the ring which comprises them may be either a single ring or a condensed ring.
- a single ring is preferable, and a ring structure is preferably a 3-membered ring to a 14-membered ring. It is more preferably a membered ring to a 7-membered ring, further preferably a 5-membered ring to a 6-membered ring, and most preferably a 5-membered ring.
- X include pyrrolyl, imidazolyl, benzimidazolyl, imidazolidinyl, pyrazolyl, pyrazolidinyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, furazanyl, thiazolyl, isothiazolyl, pyridyl, pyridinyl Group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, indolyl group, indolinyl group, isoindolyl group, isoindolinyl group, indolizinyl group, indazolyl group, quinolinyl group, isoquinolinyl group, quinolidinyl group, A quinoxalinyl group, a cinnolinyl group,
- Pyrrolyl group, imidazolyl group, benzoimidazolyl group, imidazolidinyl group, pyrazolyl group, pyrazolidinyl group, triazolyl group, and tetrazolyl group are preferable, and triazolyl group is more preferable in terms of excellent mechanical properties, corrosiveness to metals, and melt residence stability. .
- component (C) of the present invention include compounds represented by the following chemical structural formula (3) or (6).
- the content of the compound (C) having the structure represented by the formula (1) is 0.001 to 0.70% by weight, preferably 0.01 to 0.50% by weight, 0.10 More preferable is 0.30% by weight.
- the content is 0.001% by weight or more, the corrosiveness to metals is greatly improved.
- the content is 0.70% by weight or less, the mechanical strength is excellent and it is difficult to maintain high flame retardancy.
- a flammable thermoplastic resin is obtained.
- the total of (A) to (C) is 100% by weight.
- the compound (C) is the component (A). Or you may react with the compound derived from (B) component, and the structure at the time of a compounding is maintained, without reacting with the compound derived from (A) component or (B) component with the compound of (C). and it may be, but preferably be reacted with a compound derived from the compound component (a) or (B) component of (C), as a result, in which exhibits exceptional remarkable effect.
- the flame-retardant thermoplastic resin composition of the present invention has the property that it does not corrode metals during heat treatment at a heat treatment temperature of 150 to 350 ° C. and a heat treatment time of 0.01 to 10 hours, preferably a heat treatment temperature of 270 ° C. and a heat treatment time of 3 hours. Have In a heat treatment at a temperature of 270 ° C.
- the property of not corroding the metal is that a pellet or molded product of about 10 g of the resin composition is placed in a 60 mm ⁇ glass petri dish with a glass lid, and further the pellet Alternatively, a glass watch glass of 25 mm ⁇ is placed on the molded product, a copper plate having a length of 10 mm, a width of 20 mm, and a thickness of 1 mm is placed on the glass watch glass, and the glass lid is further heated to 270 ° C. Throw in the prepared gear oven GPH-200 manufactured by Tabai Espec Co., Ltd.
- the flame-retardant thermoplastic resin composition of the present invention that is, by containing a specific amount of (B) phosphinic acid salts and (C) a compound having a specific structure.
- the heat treatment temperature of 270 ° C. is also a kneading temperature range at the time of general melt kneading of polyester resins and polyamide resins or a molding temperature range at the time of injection molding. Therefore, the heat treatment temperature is 270 ° C. and the heat treatment time is 3 hours. Under the conditions, a material in which metal corrosion is observed may cause metal corrosion of the kneading screw and metal corrosion of the injection mold. In addition, under the heat treatment conditions of a heat treatment temperature of 270 ° C. and a heat treatment time of 3 hours, a material in which corrosion of the metal is observed may cause corrosion of the metal such as a terminal in contact with the molded product, which may cause contact contamination. It is a suggestion.
- the flame retardant thermoplastic resin composition of the present invention can preferably contain (D) an acidic phosphate compound.
- an acidic phosphate ester compound is a compound having a structure represented by the following formula (7). That is, it is a general term for partial ester compounds of alcohols and phosphoric acid, and is a compound having a hydroxyl group, in which hydrogen of phosphoric acid is partially substituted with an alkyl group or an aryl group.
- the low molecular weight is a colorless liquid
- the high molecular weight is a white waxy or flaky solid.
- the phosphate ester compound contained in the component (E) described later is a compound in which hydrogen of phosphoric acid is substituted with an alkyl group, an aryl group, or the like and does not have a hydroxyl group.
- group antioxidant used preferably as a stabilizer which gives the heat aging property mentioned later is the compound which substituted the alkyl group, the aryl group, etc. of hydrogen of phosphorous acid, and does not have a hydroxyl group.
- the (D) acidic phosphate compound include monomethyl acid phosphate, monoethyl acid phosphate, monoisopropyl acid phosphate, monobutyl acid phosphate, monolauryl acid phosphate, monostearyl acid phosphate, monododecyl acid phosphate, Monobehenyl acid phosphate, Dimethyl acid phosphate, Diethyl acid phosphate, Diisopropyl acid phosphate, Dibutyl acid phosphate, Lauryl acid phosphate, Distearyl acid phosphate, Didodecyl acid phosphate, Dibehenyl acid phosphate, Trimethyl acid phosphate, Triethyl acid phosphate, Triethyl acid phosphate The thing and di Mixture, mono, or a mixture of one or more thereof and the compounds of the di- and tri.
- acidic phosphate compounds that are preferably used include long-chain alkyl acid phosphate compounds such as mixtures of mono and distearyl acid phosphates.
- long-chain alkyl acid phosphate compounds such as mixtures of mono and distearyl acid phosphates.
- a flaky solid having a melting point is commercially available from ADEKA Corporation under the name “Adeka Stub” AX-71.
- the content of the (D) acidic phosphate compound is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of (A), (B) and (C), and 0.03 It is more preferably from 0.8 parts by weight, and even more preferably from 0.05 to 0.5 parts by weight.
- good mechanical properties are obtained in the following 1.0 part by weight.
- the flame retardant thermoplastic resin composition of the present invention is preferably selected from (A) a thermoplastic resin, (B) a phosphinate, a diphosphinate, a phosphinate polymer, or a diphosphinate polymer. At least one phosphinic acid salt, (C) one or more phosphorus selected from (E) a phosphoric ester compound, a phosphazene compound, and a phosphaphenanthrene compound, in addition to the compound having the structure represented by the formula (1) It is preferable to contain a nitrogen compound and / or (F) a nitrogen compound flame retardant.
- One or more phosphorus compounds selected from (E) phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds in the present invention are used as flame retardant aids that greatly improve flame retardancy in a small amount.
- Examples of the phosphoric acid ester compounds include triphenyl phosphate, tris (dimethylphenyl) phosphate, trixylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl dixylenyl phosphate, trimethyl phosphate, triethyl phosphate, condensed phosphorus
- Examples include acid esters and phosphoric ester amides. In particular, a condensed phosphate ester having excellent heat resistance is preferably used.
- condensed phosphate ester examples include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, biphenyl diphenyl phosphate, etc., and commercially available products thereof include PX-202 manufactured by Daihachi Chemical Industry Co., Ltd. One or more selected from CR-741, PX-200, PX-201, FP-500, FP-600, FP-700, and PFR manufactured by ADEKA Corporation can be used.
- phosphoric acid ester amide aromatic phosphoric acid ester amide containing nitrogen is used, and it is a powdery substance at room temperature having a high melting point, and has excellent handling properties at the time of blending.
- SP-703 manufactured by Shikoku Kasei Co., Ltd. is preferably used.
- a phosphonitrile linear polymer and / or cyclic polymer it is preferably used as a main component, especially a linear phenoxyphosphazene.
- the phosphonitrile linear polymer and / or the cyclic polymer can be synthesized by a known method described in the author, “Harabihara”, “Synthesis and Application of Phosphazene Compounds”. It can be synthesized by reacting phosphorus chloride, ammonium chloride or nitrogen gas as a nitrogen source by a known method (the cyclic product may be purified), and substituting the obtained substance with alcohol, phenol and amines. “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.
- the phosphaphenanthrene compound is a phosphorus-based flame retardant having at least one phosphaphenanthrene skeleton in the molecule, and includes HCA, HCA-HQ, BCA, SANKO-220 and M-Ester manufactured by Sanko Co., Ltd. Etc. are preferably used.
- phosphorus compounds selected from the above-mentioned (E) phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds, triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, and condensed phosphate esters are particularly preferable.
- This phosphoric acid ester compound is preferably used because it can provide a flame-retardant thermoplastic resin composition having excellent mechanical properties and retention stability.
- the (F) nitrogen compound flame retardant in the present invention is one or more selected from aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides and aromatic amides, urea and thiourea.
- (F) is a nitrogen compound-based flame retardant, and a nitrogen-containing heterocyclic compound is preferably used.
- aliphatic amine examples include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. *
- aromatic amine examples include aniline and phenylenediamine.
- nitrogen-containing heterocyclic compound examples include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and a triazine compound.
- Examples of the cyan compound include dicyandiamide.
- examples of the aliphatic amide and aromatic amide include N, N-dimethylacetamide and N, N-diphenylacetamide.
- the triazine compound exemplified in the nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound having a triazine skeleton, and includes triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, and triazine. Mention may be made of phenyltriazine, amelin, ammelide, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and melamine polyphosphate. Among these, melamine cyanurate, melamine isocyanurate, and melamine polyphosphate are preferably used.
- an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually has a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio).
- a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form.
- the salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. If the dispersibility is poor, a dispersant such as tris ( ⁇ -hydroxyethyl) isocyanurate or a known surface treatment agent such as a metal oxide such as polyvinyl alcohol and silica may be used in combination.
- the average particle diameter before and after blending with the resin of melamine cyanurate or melamine isocyanurate is preferably from 0.1 to 100 ⁇ m, preferably from the viewpoint of flame retardancy, mechanical strength and surface property of the molded product.
- the thickness is 2 to 50 ⁇ m, more preferably 0.3 to 10 ⁇ m.
- the average particle diameter is an average particle diameter measured by a 50% cumulative distribution particle diameter according to the laser micron sizer method, and commercially available products such as MC-4000 and MC-6000 manufactured by Nissan Chemical Industries, Ltd. are preferably used.
- polyphosphoric acid melamine As the polyphosphoric acid melamine, melamine phosphate, melamine pyrophosphate and melamine, melam, like melamine polyphosphate composed of melem.
- One type or two or more types may be used, and “MPP-A” manufactured by Sanwa Chemical Co., Ltd., PMP-100 and PMP-200 manufactured by Nissan Chemical Industries, Ltd. are preferably used.
- the content of (E) one or more phosphorus compounds selected from a phosphate ester compound, a phosphazene compound, and a phosphaphenanthrene compound, and / or (F) a nitrogen compound flame retardant is (E)
- the total of one or more phosphorus compounds selected from phosphate ester compounds, phosphazene compounds, and phosphaphenanthrene compounds, and (F) nitrogen compound-based flame retardants is 100 parts by weight of (A), (B), and (C).
- it is preferably 1.0 to 25 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 3 to 15 parts by weight, and particularly preferably 3 to 7 parts by weight. If it is 1 part by weight or more, a sufficient flame retardant aid effect is obtained, and if it is 25 parts by weight or less, good mechanical properties are obtained.
- a polyfunctional compound having three or more functional groups preferably one alkylene oxide unit having three or more functional groups
- One or more polyhydric alcohol compounds can be blended.
- the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups may be a low molecular compound, a polymer, a trifunctional compound, or a tetrafunctional compound. Any polyhydric alcohol compound containing at least one alkylene oxide unit having three or more functional groups such as a compound and a pentafunctional compound is preferably used.
- the functional groups of three or more functional groups are a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, It is preferably at least one selected from a silanol group and a silyl ether group, more preferably having three or more functional groups that are the same or different from these, and in particular, fluidity, mechanical properties, In terms of durability, heat resistance, and productivity, the same functional group is more preferable.
- an alkylene oxide unit of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective.
- Specific examples include methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units or isobutylene oxide units.
- the number of alkylene oxide units is 1 in terms of excellent fluidity and mechanical properties.
- the number of alkylene oxide units per functional group is preferably from 0.1 to 20, more preferably from 0.5 to 10, and even more preferably from 1 to 5.
- the polyhydric alcohol compound including one or more alkylene oxide units having three or more functional groups has a particularly remarkable effect when the (A) thermoplastic resin is a polyester resin, and reacts with the polyester resin. It may be introduced into the main chain and side chain of the component (A), and the structure at the time of blending may be maintained without reacting with the component (A).
- the viscosity of the polyhydric alcohol compound including one or more alkylene oxide units having three or more functional groups is preferably 15000 m ⁇ Pa or less at 25 ° C. from the viewpoint of fluidity. From the viewpoint, it is more preferably 5000 m ⁇ Pa or less, and particularly preferably 2000 m ⁇ Pa or less. Although there is no particular lower limit, it is preferably 100 m ⁇ Pa or more from the viewpoint of bleeding property during molding.
- the molecular weight or weight average molecular weight (Mw) of a polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is determined by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
- the value measured and quantified in terms of polymethyl methacrylate (PMMA) is preferably in the range of 50 to 10,000, more preferably in the range of 150 to 8000, in terms of fluidity. More preferably, it is in the range of 6000.
- the water content of the polyhydric alcohol compound containing one or more alkylene oxide units having three or more functional groups is preferably 1% or less. More preferably, the moisture content is 0.5% or less, even more preferably 0.1% or less, and there is no particular lower limit of moisture content. A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.
- the amount of polyhydric alcohol compounds containing alkylene oxide units having 3 or more functional groups one or more, relative to 100 parts by weight of (A) (B) (C), preferably, 0.01 to 2 0.0 part by weight, more preferably 0.05 to 1.5 parts by weight, still more preferably 0.1 to 1.0 parts by weight.
- amount 0.01 parts by weight or more, a fluidity improving effect is obtained, and when 2.0 parts by weight or less, good mechanical properties are obtained.
- a vinyl resin can be preferably blended.
- the vinyl resin in the present invention is obtained by polymerizing one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and maleimide monomers. Resins, or those obtained by graft polymerization of these monomers to rubber components such as polybutadiene rubber, or those obtained by copolymerization, such as aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid. It is a graft-polymerized or copolymerized vinyl resin containing at least 50% by weight of one or more monomer components selected from the group consisting of alkyl esters and maleimide monomers (hereinafter referred to as “ (Sometimes collectively referred to as (co) polymers).
- Examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, vinyl toluene, and divinyl benzene.
- Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
- An alkyl (meth) acrylate examples of the esters include (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate.
- maleimide monomer examples include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof.
- vinyl resins with the following components that can be copolymerized with the above vinyl resins can also be used in the present invention.
- components capable of such copolymerization include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers.
- Examples of preferred (co) polymers of vinyl resins include polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, and styrene / N-phenylmaleimide resin.
- Vinyl (co) polymers such as styrene / acrylonitrile / N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact polystyrene Styrenic resin modified with a rubbery polymer such as resin, and styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene / ethylene / butadiene / Such as styrene resin, and the like.
- polystyrene resin and acrylonitrile / styrene resin are preferable, and acrylonitrile / styrene copolymer, which is a copolymer obtained by copolymerizing acrylonitrile and styrene, is more preferable (/ indicates copolymerization).
- an acrylonitrile / styrene resin containing acrylonitrile at 15% by weight or more and less than 35% by weight is particularly preferable.
- a vinyl resin obtained by graft polymerization or copolymerization of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, or an epoxy group-containing vinyl monomer to a vinyl resin may be used.
- vinyl resins obtained by graft polymerization or copolymerization of unsaturated acid anhydrides or epoxy group-containing vinyl monomers are preferable.
- the unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.
- the epoxy group-containing vinyl monomer is a compound that shares both radically polymerizable vinyl group and epoxy group in one molecule, and specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, Examples include glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. it can. Moreover, these can be used individually or in combination of 2 or more types.
- the amount used for graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is 0.05% by weight or more based on the vinyl resin. It is preferable that Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less.
- a vinyl resin that is epoxy-modified with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid may be used.
- an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid
- a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin in order to effectively perform the epoxy modification.
- diene monomers butadiene, isoprene and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like.
- a vinyl resin composed of a multilayer structure is preferably used.
- the multilayer structure is formed of an innermost layer (core layer) and one or more outer layers (shell layer) covering the inner layer (core layer), and a vinyl-based resin is configured as one type of outer layer (shell layer), and is adjacent thereto.
- the combined layer is preferably a polymer having a so-called core-shell type structure composed of different types of polymers.
- the number of layers constituting the multilayer structure is not particularly limited, and may be two or more.
- the multilayer structure is preferably a multilayer structure having at least one rubber layer inside.
- the type of the rubber layer may be any one that is composed of a polymer component having rubber elasticity.
- a polymer component having rubber elasticity for example, an acrylic component, silicone component, styrene component, nitrile component, conjugated diene component, rubbers composed of those obtained by such a polymerized urethane component or an ethylene propylene component.
- Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and ⁇ -methylstyrene units, acrylonitrile units, It is a rubber constituted by polymerizing a nitrile component such as a methacrylonitrile unit and a conjugated diene component such as a butanediene unit or an isoprene unit. A rubber composed of a combination of two or more of these components and copolymerized is also preferably used.
- the vinyl resin used for the outer layer (shell layer) is a vinyl resin obtained by graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, or epoxy group-containing vinyl monomers. It may be a resin or a vinyl resin obtained by epoxy-modifying a vinyl resin with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid.
- Preferred examples of the multilayer structure include those in which the core layer is a dimethylsiloxane / butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer, and the core layer is a butanediene / styrene polymer.
- the outermost layer is a methyl methacrylate polymer or acrylonitrile / styrene copolymer
- the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer or an acrylonitrile / styrene copolymer.
- it is more preferable that either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.
- the weight ratio of the core to the shell is not particularly limited, but the core layer is preferably 10% by weight or more and 90% by weight or less with respect to the entire multilayer structure polymer. Furthermore, it is more preferably 30% by weight or more and 80% by weight or less.
- multilayer structure a commercially available product that satisfies the above-described conditions may be used, or it may be produced by a known method.
- Examples of commercially available multi-layer structures include “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka, “Paraloid” manufactured by Rohm and Haas, “Staffroid” manufactured by Gantz Kasei, and “Kuraray” manufactured by Kuraray Co., Ltd. Paraface "etc. are mentioned, These can use single or 2 types or more.
- a vinyl resin containing a vinyl resin as a branched chain of the graft copolymer may be used, and examples of the resin serving as a main chain include polyolefin, acrylic resin, and polycarbonate resin. Either the chain or the main chain may be modified with glycidyl methacrylate or acid anhydride.
- Specific examples include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g- PMMA), poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly (ethylene) -G-acrylonitrile / styrene (Eg-AS), polycarbonate-g Acrylonitrile / styrene (PC-g-AS) and the like ( "-g-'represents graft,” - / - "denotes copolymerization.).
- examples of the commercially available product include “Modiper” manufactured by NOF Corporation, and may be used alone or in combination with other vinyl resins.
- the compounding amount of the vinyl resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, with respect to 100 parts by weight of (A), (B) and (C). Part is particularly preferred.
- the content is 0.1 parts by weight or more, the electrical characteristics and toughness are improved, and when the content is 10 parts by weight or less, good mechanical properties are obtained.
- known flame retardants such as silicone flame retardants, phenolic resins and inorganic flame retardants can be blended within a range that does not impair the effects of the present invention.
- silicone-based flame retardant of the, silicone resin silicone oil.
- silicone resin examples include a resin having a three-dimensional network structure formed by combining structural units of SiO 2 , RSiO 3/2 , R 2 SiO, and R 3 SiO 1/2 .
- R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent.
- polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group.
- a modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned.
- the phenolic resin is a resin having a plurality of phenolic hydroxyl group, such as a novolak type, resol type and thermal reaction type resin, or these modified resins. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, a novolac type phenol resin or a melamine-modified novolac type phenol resin that is not thermally cured and does not contain a curing agent is preferable in terms of excellent flame retardancy, tensile strength, and weld strength.
- the shape of the phenolic resin, ground product, granules, flakes, powder, acicular, any such liquid can be used, if necessary, can be used alone or in combination.
- the phenolic resin is not particularly limited, and commercially available ones are used.
- the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and further oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfone. After adding a catalyst such as an acid, the mixture is heated and refluxed for a predetermined time.
- a molar ratio of phenols to aldehydes is charged into a reaction tank at a ratio of 1: 1 to 1: 2, and sodium hydroxide, aqueous ammonia, other basic substances, etc. After adding the catalyst, it can be obtained by the same reaction and treatment as the novolak type phenol resin.
- the phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy phenyl-2,2-propane, salicylic acid isoamyl, benzyl salicylate, methyl salicylate, 2,6-di -tert- butyl -p- cresol. These phenols can be used singly or in combination.
- aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can be used alone or in combination of two or more as required.
- the molecular weight of the phenol resin is not particularly limited, but is preferably 200 to 2,000 in terms of number average molecular weight, and particularly preferably in the range of 400 to 1,500 because of excellent mechanical properties, fluidity and economy.
- the molecular weight of the phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.
- the silicone flame retardant and the phenol resin have an effect of preventing the combustion from the surface of the molded product by transferring the silicone flame retardant and the phenol resin to the surface of the molded product by combustion heat.
- a Department, good flame retardancy 0.05 part by weight or more, good mechanical properties are obtained at most 2.0 parts by weight.
- inorganic flame retardant examples include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, Tin oxide salt, zinc sulfate, zinc oxide, calcium borate hydrate, zinc borate, zinc borate hydrate, zinc hydroxide ferrous oxide, ferric oxide, sulfur sulfide, stannous oxide, stannic oxide , Ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, complex oxide acid of tungsten and metalloid, ammonium sulfamate, zirconium compound, graphite, swellable graphite, fatty acid and silane cup It may be surface-treated with a ring agent or the like.
- zinc borate hydrate and swellable graphite are preferable in terms of flame retardancy, and a mixture of magnesium oxide and aluminum oxide, zinc stannate, metastannic acid, tin oxide, zinc sulfate, zinc oxide, zinc borate, zinc Ferrous oxide, ferric oxide, and sulfur sulfide are preferably used as inorganic flame retardants having excellent retention stability.
- a fluorine-based resin is blended for the purpose of preventing the flame-retardant resin composition at the time of combustion from melting and dropping (drip) and further improving the flame retardancy.
- the fluorine-based resin is a resin containing fluorine in a substance molecule.
- polytetrafluoroethylene polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra (Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc.
- polytetrafluoroethylene (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer , Polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.
- the blending amount of the fluororesin is preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of (A) (B) (C). Even more preferably, it is 0.15 to 1.0 part by weight, and if it is 0.05 part by weight or more, the effect of preventing melting and dropping during combustion is obtained, and if it is 2.0 part by weight or less, good mechanical properties are obtained. It is done.
- thermoplastic resin (A) and the resin other than the vinyl resin include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, natural rubber, thiocol rubber, polysulfide rubber, Examples include polyether rubber, epichlorohydrin rubber, ethylene-modified acid anhydrides such as maleic anhydride, glycidyl methacrylate, and modified olefin resins epoxy-modified with an epoxidizing agent. And various microstructures such as those having a cis structure, a trans structure, and the like.
- modified olefin resins epoxy-modified with ethylene such as anhydrides such as maleic anhydride, glycidyl methacrylate and epoxidizing agents, include ethylene / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, ethylene / propylene / Specific examples include maleic anhydride, ethylene / maleic anhydride, and epoxidized olefin resin obtained by epoxidizing ethylene with a peroxide. Examples of commercially available products include “bond first” manufactured by Sumitomo Chemical Co., Ltd.
- E ethylene / glycidyl methacrylate
- MH-5010 manufactured by Mitsui Chemicals, Inc.
- MH-5020 ethylene / butene-1 / maleic anhydride
- vinyl resin ethylene / butene-1 / maleic anhydride
- ethylene / butene-1 / maleic anhydride is preferably used because it greatly improves impact strength.
- the amount of the resin other than the vinyl resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of (A), (B) and (C). ⁇ 6 parts by weight is particularly preferred.
- the content is 0.1 parts by weight or more, the electrical characteristics and toughness are improved, and when the content is 10 parts by weight or less, good mechanical properties are obtained.
- alkaline earth metal soaps such as calcium stearate, barium stearate, and zinc stearate, fatty acid esters, fatty acid ester salts (one Fatty acid amides such as ethylene bisstearyl amide, polycondensates composed of ethylenediamine and stearic acid and sebacic acid, or fatty acid amides composed of polycondensate of phenylenediamine and stearic acid and sebacic acid, poly alkylene wax, acid anhydride-modified polyalkylene waxes and the above lubricant and a fluorine-based resin or fluorine known plastics mold release agent such as a mixture of compounds can be formulated.
- an alkaline earth metal soap such as zinc stearate is preferably used because it contributes to retention stability in addition to the effect of improving mold release during injection molding.
- the compounding amount of the release agent is preferably 0.01 to 1.0 part by weight, and 0.02 to 0.8 part by weight with respect to 100 parts by weight of (A), (B) and (C). More preferred is 0.03 to 0.6 parts by weight. A sufficient release effect can be obtained at 0.01 parts by weight or more, and good mechanical properties can be obtained at 1.0 parts by weight or less.
- a fiber reinforcing material can be preferably blended for the purpose of improving the mechanical strength and the heat distortion temperature.
- the fiber reinforcing material include glass fiber, aramid fiber, and carbon fiber.
- the above glass fiber is a chopped strand type or roving type glass fiber, such as a silane coupling agent such as an aminosilane compound or an epoxysilane compound, and / or urethane, vinyl acetate, bisphenol A diglycidyl ether, a novolac epoxy compound, or the like.
- Glass fibers treated with a sizing agent containing one or more epoxy compounds and the like are preferably used, and the silane coupling agent and / or sizing agent may be mixed with the emulsion liquid and used.
- the fiber diameter is 1 to 30 ⁇ m, preferably 5 to 15 ⁇ m.
- the fiber cross section is circular
- a fiber reinforcing material having an arbitrary cross section such as an elliptical glass fiber, a flat glass fiber and an eyebrow-shaped glass fiber having an arbitrary aspect ratio can be used. It is characterized by improved fluidity at the time and a molded product with less warping.
- the blending amount of the fiber reinforcement is preferably 1 to 100 parts by weight of (A), (B), and (C) from the viewpoint of fluidity during injection molding and durability of the injection molding machine or mold. 100 parts by weight, more preferably 2 to 95 parts by weight, still more preferably 3 to 90 parts by weight. The effect of improving sufficient mechanical strength and heat distortion temperature is obtained at 1 part by weight or more, and good mechanical strength and heat distortion temperature are obtained at 100 parts by weight or less.
- an inorganic filler other than the fiber reinforcement can be further blended, and the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy, or thermal deformation of the molded product of the present invention. This is to improve a part of the temperature and the like, and in particular, since it is effective in anisotropy, a molded product with less warpage can be obtained.
- inorganic fillers other than the fiber reinforcement include needle-like, granular, powdery and layered inorganic fillers, and specific examples include glass beads, milled fibers, glass flakes, california titanate, calcium sulfate.
- a molded product with little warpage can be obtained because of its effect on anisotropy.
- the inorganic filler other than the fiber reinforcing material may be subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment.
- the average particle size of the granular, powdery and layered inorganic fillers is preferably from 0.1 to 20 ⁇ m, particularly preferably from 0.2 to 10 ⁇ m from the viewpoint of impact strength.
- the amount of the inorganic filler other than the fiber reinforcement, together with the amount of fiber reinforcement from the viewpoint of durability of the molding machine and mold flowability during molding (A) (B) (C) An amount not exceeding 100 parts by weight with respect to 100 parts by weight is preferred from the viewpoint of fluidity during molding.
- an epoxy compound can be blended for the purpose of improving hydrolysis resistance, and examples thereof include glycidyl ester compounds, glycidyl ether compounds, and glycidyl ester ether compounds. it can. Further, it is also preferable to use a catalyst for promoting the reaction of the epoxy compound, and it is more preferable to use an alkali metal salt of carboxylic acid or sulfonic acid.
- the blending amount of the epoxy compound is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of (A), (B), and (C) from the viewpoint of improving hydrolysis resistance. More preferred is 02 to 2.0 parts by weight, and still more preferred is 0.03 to 1.0 parts by weight. An effect of improving sufficient hydrolysis resistance is obtained at 0.01 parts by weight or more, and good mechanical properties are obtained at 3.0 parts by weight or less.
- an oxazoline compound, a carbodiimide-modified isocyanate compound, a carbodiimide compound, and the like can be blended, and may be used alone, but in a blending amount not exceeding the above epoxy compound. It is preferable to use in combination with an epoxy compound.
- hindered phenolic antioxidants, phosphite antioxidants, and thioether-based oxidations as stabilizers that give extremely good heat aging resistance even when the composition of the present invention is exposed to high temperatures for a long period of time.
- An inhibitor can be blended, and they may be blended together.
- the blending amount is preferably 0.01 to 2.0 parts by weight, and 0.02 to 1.5 parts per 100 parts by weight of (A), (B) and (C) from the viewpoint of improving heat aging resistance. Part by weight is more preferred, and 0.03 to 1.0 part by weight is even more preferred.
- An effect of improving sufficient heat aging resistance is obtained at 0.01 parts by weight or more, and good mechanical properties are obtained at 2.0 parts by weight or less.
- the resin is mixed in various colors, weather resistance (light), and electrical conductivity are improved by blending at least one kind of carbon black, titanium oxide, and various color pigments and dyes. It is also possible.
- the blending amount of the pigment or dye is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 2 parts by weight, based on 100 parts by weight of (A), (B) and (C). Even more preferred is 0.03 to 1.0 part by weight. 0.01 parts by weight is effective in toning, weather resistance (light), and conductivity, and good mechanical properties are obtained in 3.0 parts by weight or less.
- the carbon black is preferably used.
- the treatment agent may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like.
- titanium oxide having a crystal form such as a rutile form or anatase form and having an average particle diameter of 5 ⁇ m or less is preferably used.
- the treatment agent may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like.
- the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various heat treatments in order to improve dispersibility with the flame-retardant thermoplastic resin composition of the present invention and to improve handling during production. It may be used as a mixed material which is melt blended with a plastic resin or simply blended.
- thermoplastic resin composition and molded article of the present invention.
- additives such as ultraviolet absorbers, light stabilizers, plasticizers, and antistatic agents, as long as the object of the present invention is not impaired with respect to the flame-retardant thermoplastic resin composition and molded article of the present invention.
- a material in which one or more of these are blended can also be used.
- Molded articles made of the flame-retardant thermoplastic resin composition of the present invention can be used as molded parts for mechanical mechanism parts, electrical / electronic parts or automobile parts taking advantage of high flame retardancy and excellent corrosion resistance to metals. it can.
- concrete molded products for mechanical mechanism parts, electrical / electronic parts, and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, and general household appliances.
- the flame-retardant thermoplastic resin composition of the present invention can be produced by a known method.
- a thermoplastic resin for example, (A) a thermoplastic resin, (B) a phosphinic acid salt, and (C) a compound having a specific structure, etc. are premixed and supplied to an extruder or the like, and sufficiently melt-kneaded, or a weight feeder
- the flame-retardant thermoplastic resin composition of the present invention is produced by a method in which a predetermined amount of each component is supplied to an extruder or the like using a quantitative feeder such as the above and melted and kneaded.
- the fiber filler and the inorganic filler other than the fiber reinforcement may be a method of adding a side feeder in the middle of the original loading part and the vent part of a multi-screw extruder such as a twin screw extruder. .
- liquid additives a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part
- a method of supplying with a metering pump may be used.
- the temperature condition for melt kneading is not particularly limited as long as the component (A) can be melted, and is preferably in the range of 150 to 350 ° C. 300 degrees C or less is more preferable, 280 degrees C or less is further more preferable, 260 degrees C or less is especially preferable at the point that corrosion of the metal components currently used for kneading apparatuses, such as an extruder, can be reduced, and mechanical strength and flow 200 degreeC or more is more preferable, 220 degreeC or more is further more preferable, and 240 degreeC or more is especially preferable at the point which shows the effect of reducing the amount of generated gas at the time of heating.
- thermoplastic resin composition for example, a single-screw extruder, a twin-screw extruder, a tri-screw extruder, a conical extruder, and a kneader type equipped with a “unimelt” or “dalmage” type screw. It is discharged in the form of a strand using a kneader or the like and is obtained in the form of a pellet cut with a strand cutter.
- the pellet-like flame-retardant thermoplastic resin composition thus obtained can be obtained by injection molding by a known method.
- a gas assist method As the injection molding method, a gas assist method, a two-color molding method, a sandwich molding method, an in-mold molding method, an insert molding method and an injection press molding method are known in addition to the normal injection molding method. it can.
- % and part all represent “% by weight” and “part by weight”, and “/” in the following resin names means copolymerization.
- the measuring method of each characteristic is as follows. The following were used as raw materials.
- Thermoplastic resin ⁇ A-1> Polybutylene terephthalate resin, “Toraycon” (registered trademark) 1401-X31 manufactured by Toray Industries, Inc. PBT having an intrinsic viscosity of 0.80 was used (hereinafter abbreviated as PBT resin). ).
- PBT resin Polybutylene terephthalate resin
- Similar registered trademark
- (B) Phosphinates ⁇ B-1> Aluminum diethylphosphinate, “Exolit” (registered trademark) OP1240 manufactured by Clariant Japan was used (hereinafter abbreviated as OP-1240).
- OP-1240 Aluminum diethylphosphinate
- 0.55 kg (3.82 mol) of sodium diethylphosphinate was added with stirring and heated to 80 ° C.
- a solution of 0.22 kg (0.64 mol) of aluminum sulfate and 0.88 kg of water was added while vigorously stirring, and reacted at 80 ° C. with stirring for 3 hours.
- the reaction product was filtered with suction, washed with 2.5 L of hot water and dried under reduced pressure at 120 ° C., and the solidified product was pulverized to obtain 450 g of aluminum diethylphosphinate as a white powder.
- the phosphorus content was 23.6% (calculated value 23.8%), and the aluminum content was 7.0% (calculated value 6.9%).
- ⁇ B-3> Aluminum ethylmethylphosphinate After 1.5 kg of water was charged into a 3 L reaction vessel equipped with a stirrer, 520 g (4.8 mol) of ethylmethylphosphinic acid was charged and dissolved while stirring.
- ⁇ B-4> Zinc ethylmethylphosphinate After charging 270 g (2.50 mol) of ethylmethylphosphinic acid, 102 g (1.25 mol) of zinc oxide and 300 g of acetic acid in a 1 L reaction vessel equipped with a stirrer, Stir for hours to obtain a clear solution. Subsequently, after acetic acid was removed by distillation, the resulting reaction mixture was vacuum-dried at 130 ° C., solidified, and pulverized to obtain 350 g of ethyl ethylphosphinate (melting point: 205 ° C.) as a white powder. As a result of elemental analysis, the phosphorus content was 22.0% (calculated value 22.1%), and the zinc content was 23.5% (calculated value 23.4%).
- CDA-1 A compound represented by the following formula, CDA-1 manufactured by ADEKA Corporation was used (hereinafter abbreviated as CDA-1).
- CDA-1M manufactured by ADEKA Corporation
- CDA-6 A compound represented by the following formula, CDA-6 manufactured by ADEKA Corporation was used (hereinafter abbreviated as CDA-6).
- (D) Acid phosphate ester compound ⁇ D-1> A long-chain alkyl acid phosphate compound, “Adeka Stub” AX-71 manufactured by ADEKA Corporation (hereinafter abbreviated as AX-71) was used.
- phosphate ester compound selected from a phosphate ester compound, a phosphazene compound, and a phosphaphenanthrene compound, triphenyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd. was used. (Hereinafter, abbreviated as phosphate ester compound and triphenyl phosphate).
- phosphate ester compound and triphenyl phosphate ⁇ E-2> Phosphate ester compound, condensed phosphate ester compound “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. was used (hereinafter abbreviated as phosphate ester compound, PX-200).
- phosphazene compound A phosphazene compound, “Ravitor” (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. was used (hereinafter abbreviated as “phosphazene compound”).
- phosphazene compound Phosphophenanthrene compound, M-Ester manufactured by Sanko Co., Ltd. was used (hereinafter abbreviated as “phosphaphenanthrene compound”).
- Nitrogen compound flame retardant ⁇ F-1> A salt of a triazine compound of a nitrogen-containing heterocyclic compound and cyanuric acid or isocyanuric acid, “MC-4000” manufactured by Nissan Chemical Industries, Ltd. ( Hereinafter abbreviated as MCA).
- MCA cyanuric acid or isocyanuric acid
- polyhydric alcohol polyhydric alcohol
- ⁇ G-2> Vinyl resin, styrene / acrylonitrile / glycidyl methacrylate 70 / 29.5 / 0.5 wt% epoxy-modified AS resin (hereinafter abbreviated as epoxidized AS).
- ⁇ G-3> Resin other than vinyl resin, ethylene / butene-1 / maleic anhydride copolymer, “Tuffmer” (registered trademark) MH-5020 manufactured by Mitsui Chemicals, Inc. (hereinafter referred to as MH-5020) Abbreviated).
- MH-5020 Mitsui Chemicals, Inc.
- Fluorine resin polytetrafluoroethylene, “Teflon” (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. (hereinafter abbreviated as “fluorine resin”) was used.
- Fiber reinforcing material chopped strand glass fiber having a fiber diameter of about 10 ⁇ m, and “CS3J948” manufactured by Nitto Boseki Co., Ltd. (hereinafter abbreviated as GF) were used.
- TI-144 Light stabilizer, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate ), “TINUVIN” (registered trademark) 144 manufactured by Ciba, Inc. was used (hereinafter abbreviated as TI-144).
- TI-144 Metal deactivator, N, N′-bis ⁇ 3- (3.5-di-t-butyl-4-hydroxyphenyl) propionyl ⁇ hydrozine, “IRGANOX” (registered trademark) MD1024, manufactured by Ciba (Hereinafter abbreviated as MD1024).
- Metal corrosion test with heat treatment temperature of 270 ° C and heat treatment time of 3 hours (hereinafter abbreviated as metal corrosion test) About 10 g of a flame-retardant thermoplastic resin composition pellet is placed in a 60 mm ⁇ glass petri dish with a glass lid, and a 25 mm ⁇ glass watch glass is placed on the pellet, and further 10 mm long on the glass watch glass. , horizontal 20 mm, a copper plate of thickness 1mm put, those were the samples further to the glass lid of the. The sample was placed in a gear oven GPHH-200 manufactured by Tabai Espec Co., Ltd. whose temperature was adjusted to 270 ° C. for 3 hours.
- the corrosion state of the copper plate in the sample was visually observed.
- the copper plate was corroded and changed to green due to the generation of greenish blue, which is a copper rust. Therefore, when a green discoloration was observed, it was determined that there was corrosion.
- Residence stability According to ASTM D1238-00, pellets were used and measured at a measurement temperature of 270 ° C., a load of 21.2 N, a residence time of 5 minutes (MFR 5 minutes), and a residence time of 30 minutes (MFR 30 minutes). The quotient obtained by dividing MFR 30 minutes by MFR 5 minutes was defined as the MFR change rate. The smaller the MFR change rate, the better the retention stability.
- melt mixing was performed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, and the mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.
- the obtained pellets were dried with a hot air dryer at 110 ° C. for 6 hours, and various molded products were obtained using an IS55EPN injection molding machine manufactured by Toshiba Machine. Further, various values were measured by the measurement method described above, and the results are shown in Tables 1 to 6.
- the flame-retardant thermoplastic resin composition comprising the components (A) and (B) of the present invention is obtained by the formula (C)
- the compound having the structure represented by (1) it can be said that it is a flame retardant thermoplastic resin composition that does not corrode metals while maintaining flame retardancy and physical properties.
- the comparative example 2 which contains the compound of (C) more than a specific range does not corrode a metal, it can be said that it is a flame-retardant thermoplastic resin composition which a tensile physical property halves and a physical property is impaired greatly.
- metal component in (B) component is aluminum, it is excellent in mechanical properties and flame retardancy, and when aluminum diethylphosphinate is used, it can be said that it is further excellent in mechanical properties and flame retardancy.
- thermoplastic resin composition containing a phosphorus compound (E) and / or a nitrogen compound flame retardant (F), and It can be said that the flame-retardant thermoplastic resin composition containing the fluorine-based resin can obtain higher flame retardancy while maintaining improved metal corrosivity.
- the flame retardant thermoplastic resin composition containing the polyhydric alcohol of Example 16 in Table 3 was excellent in fluidity during injection molding while maintaining improved metal corrosivity.
- the minimum lower limit pressure of Example 1 is 3.8 MPa ⁇ gauge pressure
- the flame retardant thermoplastic resin composition containing the polyhydric alcohol of Example 16 is 2.9 MPa ⁇ gauge pressure. Since the molded product was filled and the molded product was obtained at a lower pressure, the fluidity was excellent.
- the flame-retardant thermoplastic resin composition containing the epoxidized AS of Example 18 in Table 4 has a slightly improved impact strength while maintaining improved metal corrosivity, and is one of the electrical properties. Excellent tracking performance.
- the flame-retardant thermoplastic resin composition containing MH-5020 of Examples 19 and 22 in Table 4 significantly improved the impact strength while maintaining the improved metal corrosivity.
- the flame-retardant thermoplastic resin composition containing the GFs of Examples 20 to 23 in Table 4 greatly improved the tensile strength while maintaining improved metal corrosivity.
- thermoplastic resin in which the polybutylene terephthalate (A) component of Examples 27 to 28 in Table 5 is blended with “Hytrel” of the polybutylene terephthalate / polytetramethylene glycol copolymer (A).
- the composition was further improved in tensile elongation while maintaining tensile strength and flame retardancy.
- thermoplastic resin composition comprising (D) an acidic phosphate ester compound of Example 29 in Table 5 and “Hytrel” of the polybutylene terephthalate / polytetramethylene glycol copolymer of component (A) is The tensile elongation was further improved while maintaining the tensile strength and flame retardancy.
- Example 30 to 39 in Table 6 tensile properties and flame retardancy could be further improved by blending (D) acidic phosphate ester compound, (G) fluororesin and (G) GF.
- Examples 31 to 33 show that the tensile properties were significantly improved by blending PC resin as component (A).
- Examples 34 to 39 show that the mechanical properties and impact strength were improved by blending the phosphorus compound (E).
- Example 34 is excellent also in residence stability especially. From the comparisons of Example 30 and Comparative Example 11, Example 32 and Comparative Example 12, Example 36 and Comparative Example 13, the compound (C) was compounded to significantly improve the metal corrosivity and stay. It can be seen that the stability is also greatly improved.
- the corrosion state of the copper plate in the sample containing the pellet or molded product made of the flame retardant thermoplastic resin composition of the present invention was judged not to be corroded because no green discoloration was observed.
- the corrosion state of the copper plate in the sample containing pellets or molded articles made of the flame retardant thermoplastic resin composition comprising the components (A) and (B) not containing the compound (C) of the present invention is the entire surface of the copper plate. A green discoloration was observed, and it was determined that metal corrosion had progressed.
- the pellets or molded articles made of the flame-retardant thermoplastic resin composition comprising (A), (B) and (C) of the present invention are subjected to heat treatment at a heat treatment temperature of 270 ° C. and a heat treatment time of 3 hours in the present invention. It can be judged that it has the property of not corroding.
- the present invention includes a thermoplastic resin, a phosphinic acid salt and a compound having a specific structure, by the inclusion within a specific range, without using a halogen-based flame retardant has high flame retardancy
- a flame retardant thermoplastic resin composition and a molded article having excellent characteristics in which the corrosiveness to metals is greatly improved Flame retardant thermoplastic resin composition and molded article of the present invention, mechanical mechanism parts, since it is available for various applications such as electric and electronic parts or automotive parts, the industrial applicability is extremely high.
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Abstract
Description
また、ポリエステル樹脂やポリアミド樹脂は、高い融点を持つ結晶性プラスチックスであるため、溶融混練する押出機や射出成形機は高い加工温度が必要とされている。
例えば、特許文献1や特許文献2には、非ハロゲン系難燃剤として、ホスフィン酸塩と窒素含有化合物を配合することが開示されているが、難燃剤のホスフィン酸塩によって、難燃化されたポリエステル樹脂やポリアミド樹脂は、前記難燃剤から発生する腐食性ガスにより、混練装置のスクリュウが腐食、あるいは射出成形の金型が腐食する課題があった。
すなわち、かかる課題を解決するための本発明は、次の構成を特徴とするものである。
(1)(A)熱可塑性樹脂65~99重量%、(B)ホスフィン酸塩、ジホスフィン酸塩、ホスフィン酸塩のポリマー、または、ジホスフィン酸塩のポリマーから選ばれる少なくとも1種のホスフィン酸塩類1~35重量%、および(C)下記式(1)で示される構造を有する化合物0.001~0.70重量%を含有する難燃性熱可塑性樹脂組成物。
(3)(C)化合物が、下記式(2)で示される化合物である(1)または(2)に記載の難燃性熱可塑性樹脂組成物。
(4)(C)化合物が、下記式(3)で示される化合物である(1)または(2)に記載の難燃性熱可塑性樹脂組成物。
(6)さらに、(A)(B)(C)100重量部に対し、(D)酸性リン酸エステル化合物0.001~1.0重量部を含有してなる(1)~(5)のいずれかに記載の難燃性熱可塑性樹脂組成物。
(7)(E)リン酸エステル化合物、ホスファゼン化合物、およびフォスファフェナントレン化合物から選ばれる一種以上のリン系化合物、および/または、(F)窒素化合物系難燃剤を含有し、(E)リン酸エステル化合物、ホスファゼン化合物、およびフォスファフェナントレン化合物から選ばれる一種以上のリン系化合物と、(F)窒素化合物系難燃剤の総計が、
(A)熱可塑性樹脂、(B)ホスフィン酸塩、ジホスフィン酸塩、ホスフィン酸塩のポリマー、または、ジホスフィン酸塩のポリマーから選ばれる少なくとも1種のホスフィン酸塩類、(C)前記式(1)で示される構造を有する化合物
の合計を100重量部としたとき、1.0~25重量部である(1)~(6)のいずれかに記載の難燃性熱可塑性樹脂組成物。
(8)(1)~(7)のいずれかに記載の難燃性熱可塑性樹脂組成物を成形した成形品。
本発明は、(A)熱可塑性樹脂を65~99重量%含有する難燃性熱可塑性樹脂組成物である。
本発明における(A)熱可塑性樹脂とは、ポリオレフィン系樹脂(低密度ポリエチレン樹脂、高密度ポリエチレン樹脂、ポリプロピレン樹脂)、ポリエステル樹脂、ポリアミド樹脂、ポリ乳酸などの脂肪族ポリエステル樹脂、ポリスチレン樹脂、ポリアセタール樹脂、芳香族および脂肪族ポリケトン樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂、ポリイミド樹脂、熱可塑性澱粉樹脂、ポリメタクリル酸メチル樹脂等のアクリル樹脂、スチレン系樹脂(ポリスチレン樹脂、アクリロニトリル/スチレン樹脂(AS樹脂)、アクリロニトリル/ブタジエン/スチレン樹脂(ABS樹脂)、アクリロニトリル/エチレン/スチレン樹脂(AES樹脂)、アクリロニトリル/アクリル/スチレン樹脂(AAS樹脂)、塩素化ポリエチレン/アクリロニトリル/スチレン樹脂(ACS樹脂))、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン樹脂、ビニルエステル系樹脂、メチルメタクリレート/スチレン(MS樹脂)、ポリカーボネート樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、フェノキシ樹脂、ポリフェニレンエーテル樹脂、ポリ-4-メチルペンテン-1、ポリエーテルイミド樹脂、ポリビニルアルコール樹脂および熱可塑性エラストマー(ポリエーテルエステルブロック共重合体やポリエステルエステルブロック共重合体などのポリエステルエラストマー、ポリエーテルエステルアミドブロック共重合体やポリエステルアミドブロック共重合体などのポリアミドエラストマー、ポリオレフィン系エラストマー)などを挙げることができる。ポリマーアロイ樹脂も用いることができ、例えば、ポリカーボネート樹脂とABS樹脂のポリマーアロイ樹脂、ポリエステル樹脂のポリブチレンテレフタレート樹脂とABS樹脂のポリマーアロイ樹脂およびポリアミド樹脂とABS樹脂のポリマーアロイ樹脂などを挙げることができる。
これらポリアミド樹脂の重合度は、試料濃度0.01g/mlの98%濃硫酸溶液中、25℃で測定した相対粘度として、1.5~7.0の範囲のものが好ましく、特に2.0~6.0の範囲のポリアミド樹脂が好ましい。
本発明におけるホスフィン酸塩とは、下記式(4)で示される化合物である。
本発明におけるジホスフィン酸塩とは、下記式(5)で示される化合物である。
本発明では、ホスフィン酸塩類として、上記のホスフィン酸塩のポリマー、または、ジホスフィン酸塩のポリマーを使用することができる。機械物性、金属に対する腐食性、溶融滞留安定性、流動性、難燃性などに優れるという点で、金属成分としては、アルミニウムが好ましく、具体的には、エチルメチルホスフィン酸アルミニウムまたはジエチルホスフィン酸アルミニウムが好ましく、ジエチルホスフィン酸アルミニウムがより好ましい。
ホスフィン酸塩類の市販品としては、クラリアントジャパン社の「Exolit」(登録商標)OP1230やOP1240などが挙げられる。また、同社からは、(B)成分と窒素含有化合物および/またはホウ素含有化合物などを含む混合物も市販されており、市販品の例としてはOP1312が挙げられ、いずれも好ましく用いることができる。
好ましくは、下記式(2)で示される化合物である。
Xは、窒素原子を有する複素環基であれば、いずれの複素環基でもよく、環を構成する原子として、窒素原子以外に、炭素原子、酸素原子、または、硫黄原子から選ばれる原子を1種または2種以上有するものである。機械物性、金属に対する腐食性、溶融滞留安定性、流動性、難燃性などに優れるという点で、環を構成する原子の数が、3~14個であることが好ましく、5~7個であることがより好ましい。また、飽和環、部分不飽和環、芳香族環基のいずれでもよく、それらを構成する環は、単環または縮合環のいずれでもよい。機械物性、金属に対する腐食性、溶融滞留安定性、流動性、難燃性などに優れるという点で、単環が好ましく、環構造としては、3員環~14員環であることが好ましく、4員環~7員環であることがより好ましく、5員環~6員環であることがさらに好ましく、5員環であることが最も好ましい。
(B)成分のホスフィン酸塩類を含む難燃性熱可塑性樹脂組成物の課題である金属に対する腐食性を大幅に改善することができ、さらに溶融滞留安定性を大幅に改善することもできる。
化学構造式(3)で示される化合物
の市販品としては、(株)ADEKA社のCDA-1が挙げられる。また、同社からは、CDA-1と有機化合物からなるCDA-1Mも市販され、どちらも好ましく用いることができる。化学構造式(6)で示される化合物
の市販品としては、(株)ADEKA社のCDA-6が挙げられる。
本発明において、(C)前記式(1)で示される構造を有する化合物の
含有量は0.001~0.70重量%であり、0.01~0.50重量%が好ましく、0.10~0.30重量%がより好ましい。含有量が、0.001重量%以上の場合は、金属に対する腐食性が大幅に改善され、含有量が、0.70重量%以下では、機械強度に優れ、高度な難燃性を維持した難燃性熱可塑性樹脂が得られる。なお、(A)~(C)の総計は100重量%である。
本発明における(D)酸性リン酸エステル化合物とは、下記式(7)で示される構造を有する化合物である。すなわち、アルコール類とリン酸との部分エステル化合物の総称であり、リン酸の水素をアルキル基やアリール基などで一部を置換したもので、水酸基を持つ化合物である。また、形状は、低分子量のものは無色液体、高分子量のものは白色ロウ状、フレーク状固体である。
また、後述する(E)成分に含まれるリン酸エステル化合物は、リン酸の水素をアルキル基やアリール基などで置換したもので、水酸基を持たない化合物である。したがって、本発明(D)成分とは化学構造が異なり、その効果についても(D)成分とは区別して用いられる。
また、後述する耐熱エージング性を与える安定剤として好ましく用いられるホスファイト系酸化防止剤は、亜リン酸の水素をアルキル基やアリール基などを置換したもので、水酸基を持たない化合物である。したがって、本発明(D)成分とは化学構造が異なり、その効果についても(D)成分とは区別して用いられる。
前記のシリコーン系難燃剤とフェノール樹脂は、燃焼熱で成形品表面にシリコーン系難燃剤とフェノール樹脂が移動し、成形品表面から燃焼を防止する効果を有し、その配合量は、(A)(B)(C)100重量部に対し、好ましくは、0.05~2.0重量部、より好ましくは0.1~1.5重量部、さらにより好ましくは0.15~1.0重量部であり、0.05重量部以上で良好な難燃性、2.0重量部以下で良好な機械特性が得られる。
前記のフッ素系樹脂とは、物質分子中にフッ素を含有する樹脂であり、具体的には、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、(テトラフルオロエチレン/ヘキサフルオロプロピレン)共重合体、(テトラフルオロエチレン/パーフルオロアルキルビニルエーテル)共重合体、(テトラフルオロエチレン/エチレン)共重合体、(ヘキサフルオロプロピレン/プロピレン)共重合体、ポリビニリデンフルオライド、(ビニリデンフルオライド/エチレン)共重合体などが挙げられるが、中でもポリテトラフルオロエチレン、(テトラフルオロエチレン/パーフルオロアルキルビニルエーテル)共重合体、(テトラフルオロエチレン/ヘキサフルオロプロピレン)共重合体、(テトラフルオロエチレン/エチレン)共重合体、ポリビニリデンフルオライドが好ましく、特にポリテトラフルオロエチレン、(テトラフルオロエチレン/エチレン)共重合体が好ましい。
ビニル系樹脂以外に衝撃強度を改善する樹脂としては、エチレン-プロピレン共重合体、エチレン-プロピレン-非共役ジエン共重合体、エチレン-ブテン-1共重合体、天然ゴム、チオコールゴム、多硫化ゴム、ポリエーテルゴム、エピクロロヒドリンゴムおよびエチレンに無水マレイン酸などの酸無水物、グリシジルメタクリレートおよびエポキシ化剤でエポキシ変性された変性オレフィン系樹脂などが挙げられ、更に、各種の架橋度を有するものや、各種のミクロ構造、例えばシス構造、トランス構造等を有するものなどが挙げられる。前記のエチレンに無水マレイン酸などの酸無水物、グリシジルメタクリレートおよびエポキシ化剤でエポキシ変性された変性オレフィン系樹脂としては、エチレン/グリシジルメタクリレート、エチレン/ブテン-1/無水マレイン酸、エチレン/プロピレン/無水マレイン酸、エチレン/無水マレイン酸およびエチレンに過酸化物などでエポキシ化させたエポキシ化オレフィン系樹脂などが具体例として挙げられ、市販品の例としては、住友化学(株)製“ボンドファースト”E(エチレン/グリシジルメタクリレート)、三井化学(株)製MH-5010やMH-5020(エチレン/ブテン-1/無水マレイン酸)などが挙げられ、ビニル系樹脂を併用配合してもしなくとも良い。特に、エチレン/ブテン-1/無水マレイン酸が衝撃強度を大きく改善するため、好ましく用いられる。
本発明においては、さらに耐加水分解性改良を目的に、オキサゾリン化合物、カルボジイミド変性イソシアネート化合物およびカルボジイミド化合物などを配合でき、単独で用いても良いが、前記のエポキシ化合物を超えない範囲の配合量で、エポキシ化合物と併用して用いることが好ましい。
原料として、以下のものを用いた。
<A-1>ポリブチレンテレフタレート樹脂、東レ(株)社製「トレコン」(登録商標)1401-X31固有粘度が0.80のPBTを用いた(以下、PBT樹脂と略す)。
<A-2>ナイロン6樹脂、東レ(株)社製「アミラン」(登録商標)CM1010を用いた(以下、ポリアミド樹脂と略す)。
<A-3>ポリブチレンテレフタレート/ポリテトラメチレングリコール共重合体、東レ・デュポン(株)社製「ハイトレル」(登録商標)5557(以下、ハイトレルと略す)。
<A-4>ポリカーボネート樹脂、帝人化成(株)社製「パンライト」(登録商標)L-1250Y(以下、PC樹脂と略す)。
<B-1>ジエチルホスフィン酸アルミニウム、クラリアントジャパン製「Exolit」(登録商標)OP1240を用いた(以下、OP-1240と略す)。
<B-2>ジエチルホスフィン酸アルミニウム
撹拌装置付き6L反応容器に水1kgを投入した後、ジエチルホスフィン酸ナトリウム0.55kg(3.82モル)を、撹拌しながら投入し、80℃に加熱した。そこへ、硫酸アルミニウム0.22kg(0.64モル)と水0.88kgの溶液を、激しく撹拌しながら投入し、80℃、 3時間撹拌しつつ反応させた。反応物を吸引濾過した後、熱水2.5Lで洗浄し、120℃で減圧乾燥させ、固化物を粉砕し、白色粉末としてジエチルホスフィン酸アルミニウム450gを得た。元素分析の結果、リン含有量は23.6%(計算値23.8%)、アルミニウム含有量は7.0%(計算値6.9%)であった。
<B-3>エチルメチルホスフィン酸アルミニウム
撹拌装置付き3L反応容器に水1.5kgを投入した後、エチルメチルホスフィン酸520g(4.8モル)を、撹拌しながら投入し溶解させた。水酸化アルミニウム125g(1.6モル)を、激しく撹拌しながら投入し、85℃、60時間撹拌しつつ反応させた。60℃に冷却した反応物を吸引濾過した後、130℃で減圧乾燥させ、固化物を粉砕し、白色粉末としてエチルメチルホスフィン酸アルミニウム520gを得た。元素分析の結果、リン含有量は26.5%(計算値26.7%)、アルミニウム含有量は7.9%(計算値7.8%)であった。
<B-4>エチルメチルホスフィン酸亜鉛
撹拌装置付き1L反応容器に、エチルメチルホスフィン酸270g(2.50モル)、酸化亜鉛102g(1.25mol)および酢酸300gを投入した後、100℃で2時間撹拌し、透明な溶液を得た。続いて、蒸留により酢酸を除去した後、生成した反応混合物を130℃で真空乾燥させ、固化した後、粉砕して白色粉末として、エチルメチルホスフィン酸亜鉛350g(融点205℃)を得た。元素分析の結果、リン含有量は22.0%(計算値22.1%)、亜鉛含有量は23.5%(計算値23.4%)であった。
<D-1>長鎖アルキルアシッドホスフェート化合物、(株)ADEKA社製「アデカスタブ」AX-71を用いた(以下、AX-71と略す)。
<E-1>リン酸エステル化合物、大八化学工業(株)社製トリフェニルホスフェートを用いた(以下、リン酸エステル化合物、トリフェニルホスフェートと略す)。
<E-2>リン酸エステル化合物、大八化学工業(株)社製縮合リン酸エステル化合物“PX-200”を用いた(以下、リン酸エステル化合物、PX-200と略す)。
<E-3>ホスファゼン化合物、(株)伏見製薬所製「ラビトル」(登録商標)FP-110を用いた(以下、ホスファゼン化合物と略す)。
<E-4>フォスファフェナントレン化合物、三光(株)社製M-Esterを用いた(以下、フォスファフェナントレン化合物と略す)。
<F-1>含窒素複素環化合物のトリアジン系化合物とシアヌール酸またはイソシアヌール酸との塩、日産化学工業(株)社製“MC-4000”を用いた(以下、MCAと略す)。
<F-2>含窒素複素環化合物のポリリン酸メラミン、DSM社製「MELAPUR」(登録商標)200を用いた(以下、ポリリン酸メラミンと略す)。
<G-1>3つ以上の官能基を有する多官能性化合物、ポリオキシエチレンペンタエリスリトール、日本乳化剤(株)社製PNT-60U(分子量400、1官能基当たりのアルキレンオキシド(エチレンオキシド)単位数1.5を用いた(以下、多価アルコールと略す)。
<G-2>ビニル系樹脂、スチレン/アクリロニトリル/グリシジルメタクリレート=70/29.5/0.5重量%のエポキシ変性AS樹脂(以下、エポキシ化ASと略す)。
<G-3>ビニル系樹脂以外の樹脂、エチレン/ブテン-1/無水マレイン酸共重合体、三井化学(株)製「タフマー」(登録商標)MH-5020を用いた(以下、MH-5020と略す)。
<G-4>フッ素系樹脂、ポリテトラフルオロエチレン、三井・デュポンフロロケミカル(株)社製「テフロン」(登録商標)6-Jを用いた(以下、フッ素系樹脂と略す)。
<G-5>繊維強化材、繊維径約10μmのチョップドストランド状のガラス繊維、日東紡績(株)社製“CS3J948”を用いた(以下、GFと略す)。
<H-1>ヒンダードフェノール系酸化防止剤、テトラキス[メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタン、チバ社製「IRGANOX」(登録商標)1010を用いた(以下、IR-1010と略す)。
<H-2>紫外線吸収剤、2-(5-メチル-2-ヒドロキシフェニル)ベンゾトリアゾール、チバ社製「TINUVIN」(登録商標)Pを用いた(以下、TI-Pと略す)。
<H-3>光安定剤、2-(3,5-t-ブチル-4-ヒドロキシベンジル)-2-n-ブチルマロン酸ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)、チバ社製「TINUVIN」(登録商標)144を用いた(以下、TI-144と略す)。
<H-4>金属不活性剤、N,N’-ビス{3-(3.5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニル}ヒドロジン、チバ社製「IRGANOX」 (登録商標)MD1024を用いた(以下、MD1024と略す)。
<H-5>ホスファイト系酸化防止剤、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト、チバ社製「IRGAFOS」 (登録商標)168を用いた(以下、IR-168と略す)。
<H-6>メラミン、和光純薬工業(株)社製試薬を用いた。
<H-7>金属酸化物、酸化マグネシウム、和光純薬工業(株)社製試薬を用いた。
[各特性の測定方法]
本実施例、比較例においては以下に記載する測定方法によって、その特性を評価した。
東芝機械製IS55EPN射出成形機を用いて、成形温度270℃、金型温度80℃の温度条件、射出時間と保圧時間は合わせて10秒、冷却時間10秒の成形サイクル条件で試験片厚み1/8インチ(約3.2mm)厚みのASTM1号ダンベルの引張物性評価用試験片を得た。前記の機械強度評価用試験片を用い、ASTMD638(2005年)に従い、引張強度と伸びを測定し、値は3本の測定値の平均値とした。
東芝機械製IS55EPN射出成形機を用いて、成形温度270℃、金型温度80℃の条件で1/16” (約1.59mm)厚みと1/32インチ(約0.79mm)厚みの燃焼試験片を得た。
前記の燃焼試験片を用い、UL94垂直試験に定められている評価基準に従い、難燃性を評価した。難燃性はV-0>V-1>V-2の順に低下しランク付けされる。また、燃焼性に劣り上記のV-2に達せず、上記の難燃性ランクに該当しなかった材料は規格外とした。
また、燃焼試験時において、第1接炎後と第2接炎後の燃焼試験片が熱で溶融して試験片の一部が落下するか落下しないかを観察し、落下しない材料をノンドリップと評価した。
ガラス製フタ付き60mmφのガラス製シャーレに約10gの難燃性熱可塑性樹脂組成物のペレットを入れ、さらにペレットの上に25mmφのガラス製時計皿を乗せ、さらにガラス製時計皿の上に縦10mm、横20mm、厚み1mmの銅板を乗せ、さらに前記のガラス製フタをした物をサンプルとした。前記のサンプルを270℃に温調されたタバイエスペック(株)製ギヤオーブンGPHH-200に3h投入し、サンプルを室温まで冷却後、サンプル内の銅板の腐食状態を目視で観察を行った。判定方法としては、銅板は腐食されることにより、銅のサビである緑青の発生により緑色に変色するため、緑色の変色が観察される場合は、腐食ありと判断した。
東芝機械製IS55EPN射出成形機を用いて、成形温度270℃、金型温度80℃の条件で1/8インチ(約3.2mm)厚みのアイゾット衝撃試験片の射出成形を行い、ASTM D256-05に従い、ノッチ無しのアイゾット衝撃強度を測定し、値は7本の測定値の平均値とした。アイゾット衝撃強度が大きいほど耐衝撃性に優れる。
東芝機械製IS55EPN射出成形機を用いて、成形温度270℃、金型温度80℃の条件で射出成形された80mm×80mm×厚み3mmの角板を試料とし、IEC Publication112規格に示されている試験方法に従い、電解質液として0.1%塩化アンモニウム水溶液を30±5秒毎に滴下していき、破壊に至るまでの電解質液滴下数と印加電圧をプロットして50滴で破壊する印加電圧をグラフから読みとり、この数値を相対トラッキング指数(V)とした。相対トラッキング指数が大きいほど耐トラッキング性に優れる。
上記1の引張物性において、東芝機械製IS55EPN射出成形機を用いてASTM1号ダンベルを得る際、成形品が金型内で充填される最低下限圧力を求めて比較した。最低下限圧力が低いほど流動性に優れる。
ASTM D1238-00に従い、ペレットを用い、測定温度270℃、荷重21.2N、滞留時間5分(MFR5分)および滞留時間30分(MFR30分)として測定した。MFR30分をMFR5分で割った商をMFR変化率とした。MFR変化率が小さいほど滞留安定性に優れる。
スクリュー径30mm、L/D35の同方向回転ベント付き2軸押出機(日本製鋼所製、TEX-30α)を用いて、(A)熱可塑性樹脂と、(B)ホスフィン酸塩類、および、(C)前記式(1)で示される構造を有する化合物、
および必要に応じて、各種添加剤などを表1~表6に示した配合組成で混合し、2軸押出機の元込め部から添加した。なお、繊維強化材の<G-5>のガラス繊維は、元込め部とベント部の途中にサイドフィーダーを設置して添加した。さらに、混練温度270℃、スクリュー回転150rpmの押出条件で溶融混合を行い、ストランド状に吐出し、冷却バスを通し、ストランドカッターによりペレット化した。得られたペレットを110℃の熱風乾燥機で6時間乾燥後、東芝機械製IS55EPN射出成形機を用い、各種成形品を得た。さらに、前記の測定方法で種々の値を測定し、表1~表6にその結果を示した。
を含有することにより、難燃性と物性を維持しながら、金属を腐食させない難燃性熱可塑性樹脂組成物であると言える。 また、(C)の化合物を特定範囲以上に含有した比較例2は、金属を腐食させないものの、引張物性が半減し、物性を大きく損なう難燃性熱可塑性樹脂組成物であると言える。 また、(C)の化合物に替えて、公知の添加剤を配合した表2の比較例4~10は、いずれも腐食が観察され、公知の添加剤では金属の腐食性が改善されず、(C)の化合物の特異的な効果と言える。
Claims (8)
- (A)熱可塑性樹脂が、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂から選ばれる少なくとも一種である請求項1に記載の難燃性熱可塑性樹脂組成物。
- 熱処理温度270℃、熱処理時間3時間の熱処理において、金属を腐食させない性質を有する請求項1~4のいずれかに記載の難燃性熱可塑性樹脂組成物。
- さらに、(A)(B)(C)100重量部に対し、(D)酸性リン酸エステル化合物0.01~1.0重量部を含有してなる請求項1~5のいずれかに記載の難燃性熱可塑性樹脂組成物。
- (E)リン酸エステル化合物、ホスファゼン化合物、およびフォスファフェナントレン化合物から選ばれる一種以上のリン系化合物、および/または、(F)窒素化合物系難燃剤を含有し、(E)リン酸エステル化合物、ホスファゼン化合物、およびフォスファフェナントレン化合物から選ばれる一種以上のリン系化合物と、(F)窒素化合物系難燃剤の総計が、
(A)熱可塑性樹脂、(B)ホスフィン酸塩、ジホスフィン酸塩、ホスフィン酸塩のポリマー、または、ジホスフィン酸塩のポリマーから選ばれる少なくとも1種のホスフィン酸塩類、(C)前記式(1)で示される構造を有する化合物の合計を100重量部としたとき、1.0~25重量部である請求項1~6のいずれかに記載の難燃性熱可塑性樹脂組成物。 - 請求項1~7のいずれかに記載の難燃性熱可塑性樹脂組成物を成形した成形品。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01160924A (ja) | 1987-11-11 | 1989-06-23 | Merck Patent Gmbh | ナフチルアセチレン化合物 |
JPH06220124A (ja) | 1993-01-25 | 1994-08-09 | Daicel Chem Ind Ltd | エポキシ変性ブロック重合体およびその組成物 |
JPH06256417A (ja) | 1993-01-11 | 1994-09-13 | Daicel Chem Ind Ltd | 樹脂用相溶化剤および樹脂組成物 |
JPH08165353A (ja) * | 1994-12-15 | 1996-06-25 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物の製造方法 |
JP2003183509A (ja) * | 2001-12-13 | 2003-07-03 | Mitsubishi Rayon Co Ltd | 難燃性樹脂組成物およびこれを含有する繊維強化難燃性樹脂組成物 |
JP2004263188A (ja) | 2003-03-03 | 2004-09-24 | Clariant Gmbh | 熱可塑性ポリマー用の難燃剤/安定剤−組合せ物 |
JP2006528991A (ja) * | 2003-05-19 | 2006-12-28 | ポリマーズ オーストラリア プロプライアタリー リミティド | ポリエステルマスターバッチ組成物 |
WO2007128678A1 (en) * | 2006-05-02 | 2007-11-15 | Ciba Holding Inc. | Derivatives of pyrimidines as flame retardants |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05295162A (ja) * | 1992-04-23 | 1993-11-09 | Ntn Corp | 摺動材用樹脂組成物 |
JPH1160914A (ja) | 1997-08-26 | 1999-03-05 | Matsushita Electric Works Ltd | エポキシ樹脂組成物及び半導体装置 |
JP2004027061A (ja) * | 2002-06-26 | 2004-01-29 | Toray Ind Inc | 難燃性樹脂組成物およびそれからなる成形品 |
US8660035B2 (en) * | 2005-11-10 | 2014-02-25 | Apple, Inc. | Wireless relay network media access control layer control plane system and method |
CN101437886B (zh) * | 2006-05-02 | 2011-11-09 | 西巴控股有限公司 | 作为阻燃剂的嘧啶衍生物 |
-
2010
- 2010-07-05 CN CN201080006709.2A patent/CN102307947B/zh active Active
- 2010-07-05 US US13/145,678 patent/US8575246B2/en active Active
- 2010-07-05 WO PCT/JP2010/061368 patent/WO2011007687A1/ja active Application Filing
- 2010-07-05 EP EP10799746.2A patent/EP2455427B1/en active Active
- 2010-07-05 JP JP2010526102A patent/JP5609644B2/ja active Active
- 2010-07-16 TW TW099123387A patent/TWI482809B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01160924A (ja) | 1987-11-11 | 1989-06-23 | Merck Patent Gmbh | ナフチルアセチレン化合物 |
JPH06256417A (ja) | 1993-01-11 | 1994-09-13 | Daicel Chem Ind Ltd | 樹脂用相溶化剤および樹脂組成物 |
JPH06220124A (ja) | 1993-01-25 | 1994-08-09 | Daicel Chem Ind Ltd | エポキシ変性ブロック重合体およびその組成物 |
JPH08165353A (ja) * | 1994-12-15 | 1996-06-25 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物の製造方法 |
JP2003183509A (ja) * | 2001-12-13 | 2003-07-03 | Mitsubishi Rayon Co Ltd | 難燃性樹脂組成物およびこれを含有する繊維強化難燃性樹脂組成物 |
JP2004263188A (ja) | 2003-03-03 | 2004-09-24 | Clariant Gmbh | 熱可塑性ポリマー用の難燃剤/安定剤−組合せ物 |
JP2006528991A (ja) * | 2003-05-19 | 2006-12-28 | ポリマーズ オーストラリア プロプライアタリー リミティド | ポリエステルマスターバッチ組成物 |
WO2007128678A1 (en) * | 2006-05-02 | 2007-11-15 | Ciba Holding Inc. | Derivatives of pyrimidines as flame retardants |
Non-Patent Citations (1)
Title |
---|
See also references of EP2455427A4 |
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JP2011213769A (ja) * | 2010-03-31 | 2011-10-27 | Toray Ind Inc | 難燃性樹脂組成物 |
JP2013544921A (ja) * | 2010-10-28 | 2013-12-19 | クラリアント・ファイナンス・(ビーブイアイ)・リミテッド | 難燃性ポリエステル化合物 |
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JP2015529263A (ja) * | 2012-09-06 | 2015-10-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | 難燃性コポリエーテルエステル組成物、及びこれを含む物品 |
CN105246975A (zh) * | 2013-03-11 | 2016-01-13 | 科思创有限公司 | 阻燃聚碳酸酯 |
JP2016044303A (ja) * | 2014-08-20 | 2016-04-04 | 東ソー株式会社 | ポリアリーレンスルフィド樹脂組成物およびそれよりなる二次電池封口板用シール部材 |
JP2017119886A (ja) * | 2015-11-12 | 2017-07-06 | ユニチカ株式会社 | ポリアミド樹脂組成物およびそれを成形してなる成形体 |
JP2017101220A (ja) * | 2015-11-13 | 2017-06-08 | エーエムエス−パテント アクチェンゲゼルシャフト | 難燃性の脂肪族ポリケトン材料、それから製造された成形品、及びその製造方法 |
JP2017105989A (ja) * | 2015-11-13 | 2017-06-15 | エーエムエス−パテント アクチェンゲゼルシャフト | 改善された特性を有するポリケトン成形材料、それから製造された成形品、及びその製造方法 |
CN105946087A (zh) * | 2016-05-10 | 2016-09-21 | 南京林业大学 | 一种阻燃刨花板及其制备方法 |
WO2018123563A1 (ja) * | 2016-12-26 | 2018-07-05 | ユニチカ株式会社 | ポリアミド樹脂組成物、その製造方法およびそれからなる成形体 |
WO2021153414A1 (ja) | 2020-01-31 | 2021-08-05 | 東レ株式会社 | 熱可塑性ポリエステル樹脂組成物および成形品 |
CN112794867A (zh) * | 2020-11-28 | 2021-05-14 | 浙江万盛股份有限公司 | 一种二乙基次膦酸铝的合成方法 |
Also Published As
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JP5609644B2 (ja) | 2014-10-22 |
EP2455427B1 (en) | 2013-09-25 |
TWI482809B (zh) | 2015-05-01 |
US20110275743A1 (en) | 2011-11-10 |
TW201107392A (en) | 2011-03-01 |
CN102307947B (zh) | 2014-06-25 |
JPWO2011007687A1 (ja) | 2012-12-27 |
EP2455427A1 (en) | 2012-05-23 |
US8575246B2 (en) | 2013-11-05 |
CN102307947A (zh) | 2012-01-04 |
EP2455427A4 (en) | 2012-12-05 |
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