WO2010082426A1 - リン系難燃剤組成物およびそれを含有する難燃性樹脂組成物、成形体 - Google Patents
リン系難燃剤組成物およびそれを含有する難燃性樹脂組成物、成形体 Download PDFInfo
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- WO2010082426A1 WO2010082426A1 PCT/JP2009/071037 JP2009071037W WO2010082426A1 WO 2010082426 A1 WO2010082426 A1 WO 2010082426A1 JP 2009071037 W JP2009071037 W JP 2009071037W WO 2010082426 A1 WO2010082426 A1 WO 2010082426A1
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- WIPO (PCT)
- Prior art keywords
- compound
- phosphorus
- flame retardant
- aromatic
- area
- Prior art date
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 70
- 239000011574 phosphorus Substances 0.000 title claims abstract description 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011342 resin composition Substances 0.000 title claims description 19
- 239000001177 diphosphate Substances 0.000 claims abstract description 47
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- 239000000203 mixture Substances 0.000 claims abstract description 47
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 33
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
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- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to a phosphorus-based flame retardant composition for a resin, a resin composition containing the same, and a molded body comprising the same.
- a method of adding a flame retardant during the preparation of a resin molded product is employed.
- the flame retardant include an inorganic compound, an organic phosphorus compound, an organic halogen compound, and a halogen-containing organic phosphorus compound.
- organohalogen compounds and halogen-containing organophosphorus compounds exhibit excellent flame retardant effects.
- these halogen-containing compounds have the problem that they generate hydrogen halide by thermal decomposition during resin molding, corrode the mold, deteriorate the resin itself, cause coloring, and deteriorate the working environment.
- toxic gases such as hydrogen halide harmful to human bodies are generated in the event of fire or incineration.
- Such flame retardants include inorganic compounds such as magnesium hydroxide and aluminum hydroxide, and nitrogen compounds such as melamine cyanurate, melamine phosphate and melamine polyphosphate.
- inorganic compounds and nitrogen compounds have a remarkably low flame retardant effect, and in order to obtain a sufficient effect, they need to be added in a large amount, whereby the original physical properties of the resin are impaired.
- Triphenyl phosphate (TPP) is well known as a typical organic phosphate ester.
- TPP is inferior in heat resistance and has high volatility. Therefore, high-performance plastics such as engineering plastics, which have been developed in recent years, and super-engineering plastics, require a high temperature of about 300 ° C. for molding and the like, and TPP can withstand such high temperatures. Absent.
- Patent Document 2 proposes a method of solidifying and powdering the obtained aromatic diphosphate without subjecting it to a special purification treatment.
- a phosphorus compound having a hydroxyphenyl group represented by the general formula (II) is present in the aromatic diphosphate as a by-product because it is not subjected to a special purification treatment. To do.
- this by-product When an aromatic diphosphate containing this by-product is added as a flame retardant to a thermoplastic resin such as polycarbonate, it undergoes transesterification during the molding process, reacts with the molecular ends of the thermally decomposed resin, resin molding
- the problem is that the durability, physical properties, water resistance, hydrolysis resistance, and heat resistance of the resin molded product decrease as a result of lowering the molecular weight of the resin by gradually adversely affecting the product during long-term use.
- this by-product causes a transesterification with the aromatic diphosphate as a main component under a high temperature condition such as molding processing, thereby causing a further increase in by-products and a decrease in purity of the main component. .
- Patent Document 3 describes a flame retardant composition mainly composed of a phosphorus compound having a hydroxyphenyl group represented by the general formula (II) of the present invention.
- Patent Document 3 using the functional group (hydroxyphenyl group) which the compound of general formula (II) has is examined using this phosphorus compound as a reactive flame retardant of an epoxy resin.
- the additive-type flame retardant mainly composed of the aromatic diphosphate represented by the general formula (I) of the present invention the compound having a hydroxyphenyl group represented by the general formula (II) of the present invention is This is not preferable because it causes problems such as
- the present invention is a phosphor that can minimize deterioration of mechanical properties during molding of a thermoplastic resin or a long-term use of a molded product, and can impart excellent durability and flame retardancy to a resin composition. It is an object of the present invention to provide a flame retardant composition, a flame retardant resin composition containing the composition, and a molded body comprising the same.
- R 1 and R 2 are the same or different and are a lower alkyl group
- R 3 and R 4 are the same or different and are a hydrogen atom or a lower alkyl group
- Y is a bond, —CH 2 —, —C (CH 3 ) 2 —, —S—, —SO 2 —, —O—, —CO— or —N ⁇ N— group
- k represents 0 or 1
- m represents an integer of 0 to 4.
- a phosphorus-based flame retardant composition in which the content of a phosphorus compound having a hydroxyphenyl group represented by the formula is 1 area% or less as measured by gel permeation chromatography (GPC).
- thermoplastic resin even when a thermoplastic resin is molded or when a molded product is used for a long time, the deterioration of mechanical properties is minimized, and excellent durability and flame retardancy are imparted to the resin composition.
- durability means resistance to temperature, humidity, ultraviolet rays and the like.
- the phosphorus-based flame retardant composition of the present invention comprises an aromatic diphosphate compound represented by the general formula (I) (hereinafter also referred to as “aromatic diphosphate compound (I)”), and the impurity represented by the general formula (I)
- aromatic diphosphate compound (I) aromatic diphosphate compound represented by the general formula (I)
- the content of the phosphorus compound having a hydroxyphenyl group represented by II) (hereinafter also referred to as “phosphorus compound (II) having a hydroxyphenyl group”) is 1 area% or less by GPC measurement.
- the content of the phosphorus compound (II) having a hydroxyphenyl group is “1 area% or less” as measured by GPC, that the content is “over 0 area% and 1 area% or less”. Means.
- the lower limit in the content of the phosphorus compound (II) having a hydroxyphenyl group is preferably 0.01 area%, more preferably 0.001 area%, and still more preferably 0.0001 area%, and the upper limit is preferably It is 0.9 area%, More preferably, it is 0.8 area%, More preferably, it is 0.7 area%.
- the aromatic diphosphate compound (I) is preferably contained by 95 area% or more by GPC measurement.
- the phosphorus-based flame retardant composition of the present invention can be synthesized, for example, by the production method described in JP-A-5-1079 (Patent Document 1). That is, as the first step, the general formula (III):
- aromatic monohydroxy compound (III) An aromatic monohydroxy compound having a sterically hindered group at the ortho position represented by (hereinafter also referred to as “aromatic monohydroxy compound (III)”) and phosphorus oxyhalide are reacted in the presence of a Lewis acid catalyst. Then, if necessary, the organic solvent and the unreacted aromatic monohydroxy compound (III) and phosphorus oxyhalide are removed by reducing the pressure, and the general formula (IV):
- aromatic dihydroxy compound (V) an aromatic dihydroxy compound (hereinafter also referred to as “aromatic dihydroxy compound (V)”) in an organic solvent in the presence of a Lewis acid catalyst, and the organic solvent and catalyst are removed from the resulting reaction mixture. Removal of an oily substance containing the aromatic diphosphate compound (I) as a main component is obtained.
- the oily substance obtained in the second step can be made into a powder by, for example, a method described in JP-A-9-87290 (Patent Document 2). That is, in a kneader capable of controlling temperature, by applying stress at a temperature 5 to 100 ° C. lower than the melting point of the aromatic diphosphate compound (I), solidified powder is obtained as a main component, and the aromatic diphosphate compound (I) A solid or crystalline powdered phosphorus-based flame retardant composition is obtained.
- R 1 and R 2 are the same or different and represent a lower alkyl group
- R 3 represents a hydrogen atom or a lower alkyl group.
- the “lower alkyl group” for R 1 , R 2 and R 3 is a linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. Tert-butyl, n-pentyl, isopentyl, neo-pentyl and the like, and among these, a methyl group is particularly preferred.
- aromatic monohydroxy compound (III) having a sterically hindered group at the ortho position examples include 2,6-xylenol, 2,4,6-trimethylphenol, etc., and 2,6-xylenol is particularly preferable. preferable.
- examples of phosphorus oxyhalide include phosphorus oxychloride and phosphorus oxybromide, and phosphorus oxychloride is particularly preferable.
- Examples of the Lewis acid catalyst used in the reaction in the first step include aluminum chloride, magnesium chloride, titanium tetrachloride, antimony pentachloride, zinc chloride, and tin chloride. Among these, magnesium chloride is particularly preferable. Moreover, you may use these compounds in mixture of 2 or more types.
- the amount of catalyst used in the first step is 0.1% by weight or more, preferably 0.5 to 2.0% by weight, based on phosphorus oxyhalide.
- the phosphorus oxyhalide is basically used in a proportion of usually 0.5 molar equivalents relative to 1 mole of the aromatic monohydroxy compound (III).
- phosphorus oxyhalide is excessive, the by-product ratio of the aryl phosphorodihalidate increases, and a high-order condensate is by-produced with the aromatic dihydroxy compound (V) in the second step. If the amount of phosphorus oxyhalide is too small, the by-product ratio of triaryl phosphate increases, and in any case, the purity of the main component decreases.
- the reaction temperature is 50 to 250 ° C., preferably 100 to 200 ° C.
- the inside of the reaction system may be depressurized.
- a reaction solvent is not necessarily required, but it can be arbitrarily used.
- the solvent include organic solvents such as xylene, toluene, chlorobenzene, and dichlorobenzene.
- the organic solvent, unreacted aromatic monohydroxy compound (III) and phosphorus oxyhalide are removed under reduced pressure of 30 kPa or less.
- the reduced pressure is intended to remove low-boiling components, and is preferably 20 kPa or less, more preferably 10 kPa or less.
- diaryl phosphorohalidate (IV) in the reaction product is usually 99% or higher in purity and can be used in the second step without going through a purification step.
- R 4 represents a hydrogen atom or a lower alkyl group.
- the “lower alkyl group” for R 4 is a linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n -Pentyl, isopentyl, neo-pentyl and the like.
- aromatic dihydroxy compound (V) examples include hydroquinone, resorcinol, pyrocatechol, 4,4′-biphenol, 2,2 ′, 6,6′-tetramethyl-4,4′-biphenol, bisphenol.
- A bisphenol S, bisphenol F, tetramethyl bisphenol A, tetramethyl bisphenol F, 4,4′-dihydroxydiphenyl ether, 4,4′-thiodiphenol, among these, hydroquinone, resorcinol, 4,4 '-Biphenol is particularly preferred.
- Examples of the Lewis acid catalyst used in the reaction in the second step include the Lewis acid catalyst in the first step, and the Lewis acid catalyst used in the first step is not removed after the reaction in the first step.
- the reaction may be used as it is, but may be further added.
- As the Lewis acid catalyst to be added aluminum chloride is particularly preferable.
- an amine such as triethylamine or tributylamine may be used.
- the amount of the catalyst used in the second step is 0.1% by weight or more, preferably in the range of 0.5 to 5.0% by weight, based on the phosphorus oxyhalide used in the first step.
- the aromatic dihydroxy compound (V) is used at a ratio of 0.5 molar equivalent to the diaryl phosphorohalidate (IV).
- the reaction temperature is 50 to 250 ° C., preferably 100 to 200 ° C.
- the inside of the reaction system may be depressurized.
- an organic solvent may be added in order to prevent the aromatic diphosphate (I) from solidifying.
- the organic solvent those having high solubility of aromatic diphosphate (I) at high temperature and low at low temperature are preferable. Examples of such an organic solvent include, but are not limited to, toluene, xylene, chlorobenzene, dichlorobenzene, and a mixed solvent of two or more thereof.
- the treatment temperature is from room temperature to the boiling point of the aqueous solution, and the amount of the organic solvent used may be an amount that does not cause precipitation of aromatic diphosphate (I) at the treatment temperature.
- the second step is affected by the reaction of the first step. That is, the amount of the aromatic dihydroxy compound (V) in the second step is theoretically equal to 1 ⁇ 4 mole equivalent of the amount of the aromatic monohydroxy compound (III), but in actuality, 1 ⁇ 4 mole. The molar equivalent is less than the equivalent. Therefore, in the second step, the aromatic dihydroxy compound (III) is not completely consumed and remains unreacted. That is, a part of the hydroxy group of the aromatic dihydroxy compound (III) remains in the reaction system. As a result, the phosphorus compound (II) having a hydroxyphenyl group is contained in the aromatic diphosphate (I).
- the “industrial scale” means that the total amount when the aromatic dihydroxy compound (III) and the diaryl phosphorohalidate (IV) are reacted is a scale in normal industrial production.
- the scale is preferably 5 liters or more, more preferably 30 liters or more, further preferably 100 liters or more, and particularly preferably 300 liters or more.
- the total amount of these raw materials is specifically preferably 20000 liters or less, more preferably 10000 liters or less, due to limitations of the reaction apparatus.
- This is composed of an aromatic diphosphate compound (I), and preferably contains 95 area% or more by GPC measurement, and the content of phosphorus compound (II) having a hydroxyphenyl group as an impurity is 1 area% or less by GPC measurement.
- the most effective method for obtaining the phosphorus-based flame retardant compound of the invention is to convert all of the diaryl phosphorohalidate (IV) produced in the first step with a condensed phosphate ester, that is, the aromatic diphosphate compound (I).
- the stoichiometric amount required to do this, that is, the stoichiometric equivalent of the aromatic dihydroxy compound (III) to the diaryl phosphorohalidate (IV) is used in the second step.
- the theoretical amount necessary to convert all of the diaryl phosphorohalidate (IV) into a condensed phosphate ester is necessary to replace all the halogen atoms contained in the diaryl phosphorohalidate (IV) with an aryl ester group.
- such a theoretical amount can be calculated from the amount of the reaction mixture after the first step and the halogen concentration thereof.
- the phosphorus-based flame retardant compound of the present invention can be obtained by adjusting the amount of the aromatic dihydroxy compound (III) used in the second step.
- An aromatic diphosphate compound and a phosphorus compound having a hydroxyphenyl group are tetrakis (2,6-dimethylphenyl) -m-phenylene-bisphosphate, bis (2,6-dimethylphenyl) -3-hydroxyphenyl phosphate, tetrakis ( 2,6-dimethylphenyl) -p-phenylene-bisphosphate and bis (2,6-dimethylphenyl) -4-hydroxyphenyl phosphate, or tetrakis (2,6-dimethylphenyl) -4,4′-diphenylenebis
- a combination of phosphate and bis (2,6-dimethylphenyl) -4′-hydroxyphenyl-4-phenyl phosphate is preferred, and tetrakis (2,6-dimethylphenyl) -m-phenylene-bisphosphate and bis (2 , 6-Dimethylphenyl)
- a combination of 3-hydroxy-phenyl phosphate is particularly
- the phosphorus-based flame retardant compound of the present invention is represented by the general formula (VI) in addition to the main component aromatic diphosphate compound (I) and the phosphorus compound (II) having a hydroxyphenyl group as an impurity:
- Powdering step The oil obtained in the second step is subjected to stress application using a kneader generally used for kneading plastic materials at a temperature 5 to 100 ° C. lower than the melting point of the aromatic diphosphate compound (I). Can be pulverized.
- “Kneading” means that when several kinds of additives are mixed with a plastic material, a shearing force is simultaneously applied to the material and the additives to uniformly disperse the additives within the material.
- stressing is synonymous with “kneading” in that the temperature of the material supplied to the kneader is made uniform and at the same time a shearing force, that is, stress is applied to the material.
- kneaders are classified into batch types such as mixing rolls, ⁇ blade type kneaders, and intensive mixers, and continuous types such as high-speed biaxial continuous mixers and extruder type kneaders.
- batch types such as mixing rolls, ⁇ blade type kneaders, and intensive mixers
- continuous types such as high-speed biaxial continuous mixers and extruder type kneaders.
- a continuous kneader capable of simultaneously pressing the produced solidified product is preferable.
- the continuous type has a high processing capacity and is advantageous from the industrial use aspect.
- a kneader type kneader which is a kind of extruder type kneader, has a strong shearing force, has a high kneading effect, and can be continuously solidified powdered
- the model is not particularly limited as long as the model has the same effect.
- the kneader has a heating mechanism such as an electric resistance type band heater, an aluminum casting heater or a dielectric heating method, and a heating or cooling mechanism such as circulating water or oil through a jacket provided in the cylinder or a pipe provided in the screw. The temperature inside the kneader can be controlled.
- the optimum temperature range is not only the thermal physical properties of the oil to be solidified, but also the viscosity, fluidity, frictional heat during kneading, and the equipment used. Varies with characteristics.
- the temperature is generally 5 to 100 ° C., preferably 10 to 70 ° C., more preferably 10 to 50 ° C. lower than the melting point of the aromatic diphosphates. When the temperature is within this range, an appropriate stress is applied to the compound in the kneader, and complete solidification and shortening of the solidification time can be achieved. Since this method does not use a solvent in pulverization, there is no powder drying step, and there is no need to consider the purification and reuse of the solvent, which is advantageous for industrial production.
- Other methods for pulverizing the oily substance obtained in the second step include purification processes such as a recrystallization method using an organic solvent and a fractional distillation method.
- the organic solvent used in the recrystallization method include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, ketones such as acetone, methyl ethyl ketone and methyl isobutol ketone, benzene, Examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, and organic compounds that are generally used as solvents.
- the content of the phosphorus compound (II) having a hydroxyphenyl group can be further reduced as compared with pulverization using a kneader.
- the phosphorus-based flame retardant composition of the present invention is of high quality and can be used as a flame retardant for various thermoplastic resins and thermosetting resins.
- the thermoplastic resin include polyethylene resin, chlorinated polyethylene, polypropylene resin, polybutadiene resin, polystyrene resin, polyvinyl chloride resin, polyphenylene ether resin, polyphenylene sulfide resin, polycarbonate resin, ABS (Acrylonitrile-butadiene-styrene) resin, impact-resistant styrene resin, SAN (styrene-acrylonitrile) resin, ACS resin, polyamide resin, polyimide resin, polyester resin, polyacrylic resin, polymethacrylic resin, Polyetheretherketone, polyethersulfone, polysulfone, polyarylate, polyetherketones, polyethernitrile, polythioethersulfone, polybenzimidazole, polycarbodiimi , Liquid crystal polymers include such composite
- Thermosetting resins include epoxy resins, polyurethane resins, polyimide resins, phenolic resins, novolac resins, polyetherimide resins, melamine resins, urea resins, unsaturated polyesters, diallyl phthalate resins. These may be used, and these may be used alone or in combination of two or more.
- polyphenylene ether-based resins polyphenylene sulfide-based resins
- polycarbonate-based resins polycarbonate-based resins
- ABS (acrylonitrile-butadiene-styrene) -based resins can be sufficiently used by the phosphorus-based flame retardant composition of the present invention.
- Resins impact-resistant styrene resins, SAN (styrene-acrylonitrile) resins, polyamide resins, polyimide resins, polyester resins, polyacrylic resins, polymethacrylic resins, polyetheretherketone resins, polyethersulfone resins , Polysulfone, polyarylate resin, polyether ketones, polyether nitrile, polythioether sulfone, polybenzimidazole, polycarbodiimide, liquid crystal polymer, composite plastic, epoxy resin, melamine resin, Examples include engineering plastics and super engineering plastics that have high functionality such as Japanese polyester resin, and have high molding processing temperature and heat resistance temperature. Among these, polycarbonate resin, polyphenylene ether resin, rubber-modified styrene resin, polyester resin, polyamide A resin or an epoxy resin is particularly preferable.
- the flame retardant resin composition of the present invention comprises one or more resins selected from polycarbonate resins, polyphenylene ether resins, rubber-modified styrene resins, polyester resins, polyamide resins, and epoxy resins; It contains the phosphorus-type flame retardant composition of this invention, It is characterized by the above-mentioned.
- the phosphorus-based flame retardant composition of the present invention is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the resin. Particularly preferably, it is used in a proportion of 3 to 30 parts by weight.
- the flame retardant composition of the present invention may contain other components that are usually added to the resin, as necessary, within a range not impairing the effects of the present invention.
- examples of such components include other flame retardants, anti-drip agents, antioxidants, fillers, lubricants, modifiers, fragrances, antibacterial agents, pigments, dyes, heat-resistant agents, weathering agents, charged anti-blocking agents, and ultraviolet rays.
- Absorbers, stabilizers, reinforcing agents, anti-blocking agents, wood flour, starch and the like can be mentioned.
- each component is a general kneading such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a mixer, a roll, and the like.
- a known method such as melt kneading using an apparatus may be used.
- Resin having a high molding temperature for example, in one embodiment, a resin molded at 160 ° C. or higher, in a more preferable embodiment, a resin molded at 180 ° C. or higher, and in a particularly preferable embodiment, molded at 200 ° C. or higher.
- the phosphorus-based flame retardant composition of the present invention can be advantageously used.
- the phosphorus-based flame retardant composition of the present invention is a high-quality material that has excellent heat resistance and coloring resistance without generating gas at the high processing temperature when added to a resin as a flame retardant and processed on a molding machine. Can be provided.
- the phosphorus-based flame retardant composition of the present invention can be added to a resin and molded to provide a desired molded product. Therefore, the molded article of the present invention is characterized by comprising the flame retardant resin composition of the present invention.
- the method for molding the flame-retardant resin composition of the present invention is not particularly limited, and for example, it is molded into a desired shape using a molding machine such as an injection molding machine, an extrusion molding machine, a blow molding machine, or an inflation molding machine.
- a molding machine such as an injection molding machine, an extrusion molding machine, a blow molding machine, or an inflation molding machine.
- Known methods such as
- the ratio of each component in the obtained composition is expressed as a percentage (area%) of the area of each component measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Solvent Tetrahydrofuran (for industrial use)
- Solvent flow rate 0.8 ml / min
- Detector RI (Built-in main body, polarization type differential refractometer) Range: 16
- Sample solution injection volume 100 ⁇ l (loop tube)
- Sample solution solution obtained by dissolving about 0.05 g of sample in 10 ml of tetrahydrofuran
- Data processing device manufactured by Tosoh Corporation, model: SC-8010
- Data processing conditions START TIME 10.0min
- Example 1 First Step Into a 1 liter four-necked flask equipped with a stirrer, thermometer, dropping device (funnel) and hydrochloric acid recovery device (condenser connected with water scrubber), 2,6- 244 g of xylenol, 20 g of xylene as a solvent and 1.5 g of magnesium chloride as a catalyst were charged. The obtained mixed solution was heated with stirring, and when the temperature of the mixed solution reached 120 ° C., 153 g of phosphorus oxychloride was added dropwise over about 2 hours. After completion of the addition, the temperature of the mixed solution was gradually heated to 180 ° C.
- the oil phase of the obtained mixed solution was washed with 130 g of water at a liquid temperature of 85 ° C. to obtain 430 g of an oil phase (the concentration of aromatic diphosphate (I) was about 80% by weight).
- Xylene was removed from the obtained oil phase under reduced pressure, and then vacuum steam distillation was performed at a temperature of 140 ° C. and a pressure of 6 kPa to obtain 330 g of an oily substance containing the aromatic diphosphate compound (I).
- the product was filled with 320 g, cooled to a temperature of 60 ° C. with stirring at a low rotation speed (about 100 rpm), and kept at the same temperature (60 ° C.) using a hot water bath.
- 0.1% by weight of a crystalline aromatic diphosphate compound (I) as a crystal nucleus was added to the solidified object (oil) and stirred at a rotation speed of 200 rpm. The thing completely solidified.
- the obtained solidified product 320 g was a white powder and had a melting point of 98 to 101 ° C. Moreover, when the composition was measured by gel permeation chromatography (GPC), the aromatic diphosphate (I) represented by the compound (1) was 96.6 area%, and the hydroxyphenyl represented by the compound (2). The phosphorus compound (II) having a group is 0.7 area%, the aromatic monophosphate (VI) represented by the compound (7) is 2.1 area%, and the aromatic triphosphate represented by the compound (8) (VII) was 0.6 area% (see the following structural formula). The obtained results are shown in Table 1 together with the raw materials used.
- Example 2 Except for using a 20-liter four-necked flask as a reaction vessel, using 5856 g of 2,6-xylenol as an aromatic monohydroxy compound (III), 480 g of xylene as a solvent, 36 g of magnesium chloride and 3672 g of phosphorus oxychloride as a catalyst.
- a reaction mixture containing di (2,6-xylyl) phosphorochloridate as diaryl phosphorohalidate (IV) was obtained.
- the chlorine content of the reaction mixture was 10.6% by weight.
- Example 2 Except for adding 2160 g of xylene, 216 g of 35% aqueous hydrochloric acid, 3360 g of water, 120 g of 28% aqueous sodium hydroxide and 3120 g of water to the obtained crude product, and using 3120 g of washing water, the same procedure as in Example 1 was performed. Purification was carried out to obtain 7960 g of an oily substance containing the aromatic diphosphate compound (I). In addition, a powdering step was performed in the same manner as in Example 1 except that a 20-liter four-necked flask was used and 7920 g of an oily substance containing the aromatic diphosphate compound (I) was used. Got.
- the obtained white powder had a melting point of 98-101 ° C.
- the aromatic diphosphate (I) represented by the compound (1) has 96.2 area%, and has a hydroxyphenyl group represented by the compound (2).
- the phosphorus compound (II) is 0.8 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.3 area%
- the aromatic triphosphate (VII) represented by the compound (8) is It was 0.7 area%.
- Table 1 The obtained results are shown in Table 1 together with the raw materials used.
- Example 3 320 g of white powder was obtained in the same manner as in Example 1 except that hydroquinone was used instead of resorcinol.
- the obtained white powder had a melting point of 171 to 173 ° C.
- the chlorine content of the reaction mixture in the first step was 10.6% by weight.
- the aromatic diphosphate (I) represented by the compound (3) has 96.6 area%, and has a hydroxyphenyl group represented by the compound (4).
- Phosphorus compound (II) is 0.7 area%
- aromatic monophosphate (VI) represented by compound (7) is 2.1 area%
- aromatic triphosphate (VII) represented by compound (9) is It was 0.6 area% (see the following structural formula).
- the obtained results are shown in Table 1 together with the raw materials used.
- Example 4 7920 g of white powder was obtained in the same manner as in Example 2 except that hydroquinone was used instead of resorcinol.
- the obtained white powder had a melting point of 171 to 173 ° C.
- the chlorine content of the reaction mixture in the first step was 10.6% by weight.
- the aromatic diphosphate (I) represented by the compound (3) has 96.4 area%, and has a hydroxyphenyl group represented by the compound (4).
- the phosphorus compound (II) is 0.7 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.2 area%
- the aromatic triphosphate (VII) represented by the compound (9) is It was 0.7 area%.
- Table 1 The obtained results are shown in Table 1 together with the raw materials used.
- Example 5 354 g of white powder was obtained in the same manner as in Example 1 except that 90 g of 4,4′-biphenol was used in place of resorcinol and dichlorobenzene was used in place of xylene.
- the obtained white powder had a melting point of 187 ° -189 ° C.
- the chlorine content of the reaction mixture in the first step was 10.4% by weight.
- the aromatic diphosphate (I) represented by the compound (5) has 96.6 area%, and has a hydroxyphenyl group represented by the compound (6).
- the phosphorus compound (II) is 0.7 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.1 area%
- the aromatic triphosphate (VII) represented by the compound (10) is It was 0.6 area% (see the following structural formula).
- the obtained results are shown in Table 1 together with the raw materials used.
- Example 6 8800 g of white powder was obtained in the same manner as in Example 2 except that 2,150 g of 4,4′-biphenol was used in place of resorcinol and dichlorobenzene was used in place of xylene.
- the obtained white powder had a melting point of 187 ° -189 ° C.
- the chlorine content of the reaction mixture in the first step was 10.4% by weight.
- the aromatic diphosphate (I) represented by the compound (5) has 96.2 area%, and has a hydroxyphenyl group represented by the compound (6).
- the phosphorus compound (II) is 0.7 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.4 area%
- the aromatic triphosphate (VII) represented by the compound (10) is It was 0.7 area%.
- the obtained results are shown in Table 1 together with the raw materials used.
- Phosphorus compound (II) is 1.2 area%, aromatic monophosphate (VI) represented by compound (7) is 1.8 area% and aromatic triphosphate (VII) represented by compound (8) is It was 0.4 area%.
- the obtained results are shown in Table 1 together with the raw materials used.
- the phosphorus compound (II) is 2.5 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.0 area%
- the aromatic triphosphate (VII) represented by the compound (8) is It was 0.5 area%.
- the obtained results are shown in Table 1 together with the raw materials used.
- Example 3 The same as Example 3 except that 55 g of hydroquinone (1/4 mol amount relative to the number of moles of 2,6-xylenol as the aromatic monohydroxy compound (III)) was used as the aromatic dihydroxy compound (V). As a result, 8005 g of white powder was obtained. The obtained white powder had a melting point of 171 to 173 ° C. The chlorine content of the reaction mixture in the first step was 10.6% by weight.
- the aromatic aromatic diphosphate (I) represented by the compound (5) was 96.4 area%
- the hydroxyphenyl group represented by the compound (6) was The phosphorus compound (II) having 1.2 area%
- the aromatic monophosphate (VI) represented by the compound (7) is 2.0 area%
- the aromatic triphosphate (VII) represented by the compound (10) was 0.4 area%.
- Table 1 The obtained results are shown in Table 1 together with the raw materials used.
- modified PPE resin manufactured by Nippon GE Plastics, trade name: Noryl 731
- PC / ABS alloy resin manufactured by Daicel Polymer Co., Ltd., trade name: Novalloy S-1500
- ABS resin manufactured by Daicel Polymer Co., Ltd.
- fluororesin trade name: Teflon (registered trademark) 6-J, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.
- the durability test was performed using the following testing machine.
- Tables 2 to 4 it is described that after Rainbow 6HR treatment and after Rainbow 24HR treatment, respectively, and the ratio with respect to the initial value is added as a maintenance rate (%).
- the molded product of the flame-retardant resin composition containing the phosphorus-based flame retardant composition of the present invention is excellent in Izod impact strength and melt flow rate, and particularly excellent in durability to temperature and humidity.
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Abstract
Description
このような難燃剤としては、水酸化マグネシウムや水酸化アルミニウムなどの無機系化合物、メラミンシアヌレート、メラミンホスフェートやメラミンポリホスフェートなどの窒素系化合物がある。しかし、これらの無機系化合物や窒素系化合物は難燃効果が著しく低く、充分な効果を得るためには多量に添加する必要があり、それによって樹脂本来の物性が損なわれるという問題がある。
したがって、近年、開発が進んでいるエンジアリングプラスチック、さらにはスーパーエンジニアリングプラスチックなどの高機能プラスチックでは、成形加工などに300℃前後の高い温度が必要とされ、TPPはこのような高温には耐えられない。
そこで、特許文献2では、得られた芳香族ジホスフェートを特別な精製処理に付することなく固化させ粉末化する方法が提案された。
しかしながら、特許文献2に記載の方法では、特別な精製処理に付さないために、副生成物として一般式(II)で表されるヒドロキシフェニル基を有するリン化合物が芳香族ジホスフェート中に存在する。
また、この副生成物は、成形加工などの高温条件において、主成分である芳香族ジホスフェートとエステル交換を起こし、さらなる副生成物の増加を引き起こし、主成分の純度が低下するという問題もある。
しかしながら、本発明の一般式(I)で表される芳香族ジホスフェートを主成分とする添加型難燃剤では、本発明の一般式(II)で表されるヒドロキシフェニル基を有する化合物は、上記のような問題を引き起こす原因となり好ましくない。
で表される芳香族ジホスフェート化合物からなり、かつ不純物として一般式(II):
で表されるヒドロキシフェニル基を有するリン化合物の含有量がゲル透過クロマトグラフィー(GPC)測定で1面積%以下であることを特徴とするリン系難燃剤組成物が提供される。
ここで、ヒドロキシフェニル基を有するリン化合物(II)の含有量がGPC測定で「1面積%以下である」とは、その含有量が「0面積%を超えかつ1面積%以下である」ことを意味する。ヒドロキシフェニル基を有するリン化合物(II)の含有量における下限は、好ましくは0.01面積%、より好ましくは0.001面積%、さらに好ましくは0.0001面積%であり、その上限は好ましくは0.9面積%、より好ましくは0.8面積%、さらに好ましくは0.7面積%である。
芳香族ジホスフェート化合物(I)は、GPC測定で95面積%以上含まれるのが好ましい。
すなわち、第1工程として、一般式(III):
で表されるオルト位に立体障害基を有する芳香族モノヒドロキシ化合物(以下、「芳香族モノヒドロキシ化合物(III)」ともいう)とオキシハロゲン化リンとをルイス酸触媒の存在下で反応させて、次いで必要に応じて減圧により有機溶剤や未反応の芳香族モノヒドロキシ化合物(III)およびオキシハロゲン化リンを除去し、一般式(IV):
で表されるジアリールホスホロハリデート(以下、「ジアリールホスホロハリデート(IV)」ともいう)を得る。
で表される芳香族ジヒドロキシ化合物(以下、「芳香族ジヒドロキシ化合物(V)」ともいう)とをルイス酸触媒の存在下、有機溶剤中で反応させ、得られた反応混合物から有機溶剤および触媒を除去して、主成分として芳香族ジホスフェート化合物(I)を含む油状物を得る。
すなわち、温度制御可能なニーダー中、芳香族ジホスフェート化合物(I)の融点より5~100℃低い温度で応力付加を行って固化粉末化することにより、主成分として芳香族ジホスフェート化合物(I)を含む、固体または結晶性粉末状のリン系難燃剤組成物が得られる。
1.第1工程
R1、R2およびR3の「低級アルキル基」とは、直鎖または分枝状の炭素数1~5のアルキル基であって、例えばメチル、エチル、プロピル、イソプロピル、n-ブチル、イソブチル、tert-ブチル、n-ペンチル、イソペンチル、neo-ペンチルなどが挙げられ、これらの中でもメチル基が特に好ましい。
第1工程の触媒の使用量は、オキシハロゲン化リンに対して0.1重量%以上、好ましくは0.5~2.0重量%の範囲である。
R4の「低級アルキル基」とは、直鎖または分枝状の炭素数1~5のアルキル基であって、例えばメチル、エチル、プロピル、イソプロピル、n-ブチル、イソブチル、tert-ブチル、n-ペンチル、イソペンチル、neo-ペンチルなどが挙げられる。
第2工程の触媒の使用量は、第1工程で使用されたオキシハロゲン化リンに対して0.1重量%以上、好ましくは0.5~5.0重量%の範囲である。
この時、芳香族ジホスフェート(I)が固体化することを防止するために、有機溶剤を添加してもよい。
有機溶剤としては、高温での芳香族ジホスフェート(I)の溶解度が高く、低温で低いものが好ましい。このような有機溶剤としては、例えば、トルエン、キシレン、クロロベンゼン、ジクロロベンゼンおよびこれらの2種以上の混合溶剤が挙げられるが、これらに限定されるものではない。
また、処理温度は、室温から前記水溶液の沸点以下までであり、有機溶剤の使用量は処理温度において、少なくとも芳香族ジホスフェート(I)の析出が起こらない量であればよい。
また、それらの原料の合計量は、反応装置の制約などから、具体的には、好ましくは20000リットル以下、より好ましくは10000リットル以下である。
このような理論量は、具体的には、第1工程後の反応混合物の量およびそのハロゲン濃度から算出することができる。
上記のように、第2工程における芳香族ジヒドロキシ化合物(III)の使用量を調整することにより、本発明のリン系難燃化合物を得ることができる。
で表される芳香族モノホスフェート(以下、「芳香族モノホスフェート(VI)」ともいう)および、一般式(VII):
で表される芳香族トリホスフェート(以下、「芳香族トリホスフェート(VII)」ともいう)も同時に生成する。
しかしながら、これらの芳香族モノホスフェート(VI)および芳香族トリホスフェート(VII)はヒドロキシフェニル基を有さないので、樹脂には前述のような悪影響を何ら及ぼさない。
第2工程において得られた油状物を、芳香族ジホスフェート化合物(I)の融点より5~100℃低い温度で、一般にプラスチック材料の混練に使用されるニーダーを用いて応力付加を行って粉末化することができる。
「混練」とは、プラスチック材料に数種の添加剤を混ぜ合わせる場合、材料と添加剤に同時に剪断力を与え、添加剤を材料内部に均一に分散させることをいう。
また、「応力付加」とは、ニーダーに供給される材料の温度を均一にすると同時に、材料に剪断力、すなわち応力を付与する点で「混練」と同義である。
また、ニーダーは電気抵抗型バンドヒーター、アルミニウム鋳込みヒーターまたは誘電加熱方式などの加熱機構、およびシリンダに設けたジャケット部やスクリュー内に設けたパイプに水または油を流通させるなどの加熱または冷却機構を備え、ニーダー内部の温度を制御することができる。
再結晶法で使用する有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノールなどのアルコール類、アセトン、メチルエチルケトン、メチルイソブトルケトンなどのケトン類、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素、クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素、一般的に溶剤として用いられる有機化合物が挙げられる。
この再結晶法では、ニーダーを用いた粉末化よりもさらに、ヒドロキシフェニル基を有するリン化合物(II)の含有量を少なくすることができる。
熱可塑性樹脂としては、例えば、ポリエチレン系樹脂、塩素化ポリエチレン、ポリプロピレン系樹脂、ポリブタジエン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド系樹脂、ポリカーボネート系樹脂、ABS(アクリロニトリル-ブタジエン-スチレン)系樹脂、耐衝撃性スチレン系樹脂、SAN(スチレン-アクリロニトリル)系樹脂、ACS樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエステル系樹脂、ポリアクリル系樹脂、ポリメタクリル系樹脂、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリスルホン、ポリアリレート、ポリエーテルケトン類、ポリエーテルニトリル、ポリチオエーテルスルホン、ポリベンズイミダゾール、ポリカルボジイミド、液晶ポリマー、複合化プラスチックなどが挙げられ、これらは1種を単独で、2種以上を混合して用いることができる。
本発明のリン系難燃剤組成物は、難燃剤として樹脂に添加して成形機で加工する際に、その高い処理温度でガスを発生することなく、耐熱性、耐着色性に優れた高品質な成形品を提供することができる。
したがって、本発明の成形体は、本発明の難燃性樹脂組成物からなることを特徴とする。
分析装置:東ソー株式会社製、型式:HLC-8020
カラム:東ソー株式会社製、型式:TSKGEL G1000HXL(30cm)2本
カラム槽温度:40℃
溶剤:テトラヒドロフラン(工業用)
溶剤流量:0.8ml/分
検出器:RI(本体内蔵、偏光型示差屈折計)
レンジ:16
試料溶液注入量:100μl(ループ管)
試料溶液:試料約0.05gをテトラヒドロフラン10mlに溶解した溶液
データ処理装置:東ソー株式会社製、型式:SC-8010
データ処理条件:START TIME 10.0min
STOP TIME 25.0min
WIDTH 10
SENSITIVITY 0.8
DRIFT 0.1
MINIMUM AREA 0.0
MINIMUM HEIGHT 0.0
1.第1工程
攪拌機、温度計、滴下装置(ロート)および塩酸回収装置(水スクラバーを連結したコンデンサー)を備えた1リットルの4つ口フラスコに、芳香族モノヒドロキシ化合物(III)として2,6-キシレノール244g、溶剤としてキシレン20gおよび触媒として塩化マグネシウム1.5gを充填した。得られた混合溶液を攪拌しながら加熱し、混合溶液の温度が120℃に達した時点で、オキシ塩化リン153gを約2時間かけて滴下により添加した。添加終了後、混合溶液の温度を180℃まで2時間かけて徐々に加熱昇温し、反応させて、発生する塩化水素(塩酸ガス)68gを水スクラバーから回収した。その後、同温度(180℃)でフラスコ内の圧力を徐々に20kPaまで減圧し、1時間かけてキシレンや未反応のオキシ塩化リンおよび2,6-キシレノールを除去し、ジアリールホスホロハリデート(IV)としてジ(2,6-キシリル)ホスホロクロリデートを含む反応混合物322g(収率99.2%)を得た。また、反応混合物の塩素含有率は10.7重量%であった。
次に、第1工程で得られた反応混合物に、芳香族ジヒドロキシ化合物(V)としてレゾルシノール53.5g(ジ(2,6-キシリル)ホスホロクロリデートに対して化学量論的に等量である量)、追加触媒として塩化アルミニウム4.2gを加えた。得られた混合溶液を攪拌しながら加熱し、混合溶液の温度を180℃まで2時間かけて徐々に加熱昇温し、脱塩酸反応を行なった。同温度(180℃)で2時間反応させ、フラスコ内の圧力を徐々に20kPaまで減圧し、その減圧下でさらに2時間反応させ、芳香族ジホスフェート化合物(I)の粗製物を得た。
得られた粗製物を85℃に加熱し、キシレン90g、35%塩酸水9gおよび水140gを加え、同温度(85℃)で1時間撹拌し、静置後に水相を分離した。
得られた粗製物と溶剤(キシレン)との混合物(粗製物濃度は約80重量%)に、28%水酸化ナトリウム水溶液5gおよび水130gを加えた。得られた混合溶液を85℃で1時間攪拌し、静置後に水相を分離した。
次いで、得られた混合溶液の油相を、液温85℃において水130gで洗浄し、油相430g(芳香族ジホスフェート(I)の濃度は約80重量%)を得た。得られた油相から減圧下でキシレンを除去し、その後温度140℃、圧力6kPaで減圧水蒸気蒸留を行い、芳香族ジホスフェート化合物(I)を含む油状物330gを得た。
回転数表示機能付き撹拌機(新東科学株式会社製、型式:HEIDON TYPE3000H型)および温度計を備えた1リットルの4つ口フラスコに、芳香族ジホスフェート化合物(I)を含む油状物320gを充填し、低回転(回転数100rpm程度)で攪拌しながら温度60℃まで放冷し、湯浴を用いて同温度(60℃)に保持した。
次いで、結晶核として結晶状の芳香族ジホスフェート化合物(I)を固化対象物(油状物)に対して0.1重量%を添加し、回転数200rpmで攪拌したところ、所要時間8分で油状物が完全に固化した。
また、ゲル透過クロマトグラフィー(GPC)により、その組成を測定したところ、化合物(1)で表される芳香族ジホスフェート(I)が96.6面積%、化合物(2)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.7面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.1面積%、および化合物(8)で表される芳香族トリホスフェート(VII)が0.6面積%であった(下記構造式参照)。
得られた結果を使用した原料と共に表1に示す。
反応容器として20リットルの4つ口フラスコを用い、芳香族モノヒドロキシ化合物(III)として2,6-キシレノール5856g、溶剤としてキシレン480g、触媒として塩化マグネシウム36gおよびオキシ塩化リン3672gを用いたこと以外は実施例1の第1工程と同様にして、ジアリールホスホロハリデート(IV)としてジ(2,6-キシリル)ホスホロクロリデートを含む反応混合物7741g(収率99.4%)を得た。また、反応混合物の塩素含有率は10.6重量%であった。
また、芳香族ジヒドロキシ化合物(V)としてレゾルシノール1273gおよび追加触媒として塩化アルミニウム101gを用いたこと以外は実施例1の第2工程と同様にして、芳香族ジホスフェート化合物(I)の粗製物8200gを得た。
また、20リットルの4つ口フラスコを用いたこと、および芳香族ジホスフェート化合物(I)を含む油状物7920gを用いたこと以外は実施例1と同様にして粉末化工程を行い、白色粉末7920gを得た。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(1)で表される芳香族ジホスフェート(I)が96.2面積%、化合物(2)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.8面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.3面積%および化合物(8)で表される芳香族トリホスフェート(VII)が0.7面積%であった。
得られた結果を使用した原料と共に表1に示す。
レゾルシノールの代わりにハイドロキノンを用いたこと以外は実施例1と同様にして、白色粉末320gを得た。
得られた白色粉末は、融点171~173℃であった。
なお、第1工程の反応混合物の塩素含有率は10.6重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(3)で表される芳香族ジホスフェート(I)が96.6面積%、化合物(4)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.7面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.1面積%および化合物(9)で表される芳香族トリホスフェート(VII)が0.6面積%であった(下記構造式参照)。
得られた結果を使用した原料と共に表1に示す。
レゾルシノールの代わりにハイドロキノンを用いたこと以外は実施例2と同様にして、白色粉末7920gを得た。
得られた白色粉末は、融点171~173℃であった。
なお、第1工程の反応混合物の塩素含有率は10.6重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(3)で表される芳香族ジホスフェート(I)が96.4面積%、化合物(4)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.7面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.2面積%および化合物(9)で表される芳香族トリホスフェート(VII)が0.7面積%であった。
得られた結果を使用した原料と共に表1に示す。
レゾルシノールの代わりに4,4’-ビフェノール90gを用い、キシレンの代わりにジクロロベンゼンを用いたこと以外は実施例1と同様にして、白色粉末354gを得た。
得られた白色粉末は、融点187~189℃であった。
なお、第1工程の反応混合物の塩素含有率は10.4重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(5)で表される芳香族ジホスフェート(I)が96.6面積%、化合物(6)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.7面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.1面積%および化合物(10)で表される芳香族トリホスフェート(VII)が0.6面積%であった(下記構造式参照)。
得られた結果を使用した原料と共に表1に示す。
レゾルシノールの代わりに4,4’-ビフェノール2150gを用い、キシレンの代わりにジクロロベンゼンを用いたこと以外は実施例2と同様にして、白色粉末8800gを得た。
得られた白色粉末は、融点187~189℃であった。
なお、第1工程の反応混合物の塩素含有率は10.4重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(5)で表される芳香族ジホスフェート(I)が96.2面積%、化合物(6)で表されるヒドロキシフェニル基を有するリン化合物(II)が0.7面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.4面積%および化合物(10)で表される芳香族トリホスフェート(VII)が0.7面積%であった。
得られた結果を使用した原料と共に表1に示す。
芳香族ジヒドロキシ化合物(V)としてレゾルシノール55g(芳香族モノヒドロキシ化合物(III)としての2,6-キシレノールのモル数に対して4分の1モル量)を用いたこと以外は実施例1と同様にして、白色粉末322gを得た。
得られた白色粉末は、融点98~101℃であった。
なお、第1工程の反応混合物の塩素含有率は10.7重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(1)で表される芳香族ジホスフェート(I)が96.6面積%、化合物(2)で表されるヒドロキシフェニル基を有するリン化合物(II)が1.2面積%、化合物(7)で表される芳香族モノホスフェート(VI)が1.8面積%および化合物(8)で表される芳香族トリホスフェート(VII)が0.4面積%であった。
得られた結果を使用した原料と共に表1に示す。
芳香族ジヒドロキシ化合物(V)としてレゾルシノール1320g(芳香族モノヒドロキシ化合物(III)としての2,6-キシレノールのモル数に対して4分の1モル量)を用いたこと以外は実施例2と同様にして、白色粉末8000gを得た。
得られた白色粉末は、融点98~101℃であった。
なお、第1工程の反応混合物の塩素含有率は10.6重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(1)で表される芳香族ジホスフェート(I)が95.5面積%、化合物(2)で表されるヒドロキシフェニル基を有するリン化合物(II)が2.5面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.0面積%および化合物(8)で表される芳香族トリホスフェート(VII)が0.5面積%であった。
得られた結果を使用した原料と共に表1に示す。
芳香族ジヒドロキシ化合物(V)としてハイドロキノン55g(芳香族モノヒドロキシ化合物(III)としての2,6-キシレノールのモル数に対して4分の1モル量)を用いたこと以外は実施例3と同様にして、白色粉末8005gを得た。
得られた白色粉末は、融点171~173℃であった。
なお、第1工程の反応混合物の塩素含有率は10.6重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(3)で表される芳芳香族ジホスフェート(I)が96.3面積%、化合物(4)で表されるヒドロキシフェニル基を有するリン化合物(II)が1.5面積%、化合物(7)で表される芳香族モノホスフェート(VI)が1.8面積%および化合物(9)で表される芳香族トリホスフェート(VII)が0.4面積%であった。
得られた結果を使用した原料と共に表1に示す。
芳香族ジヒドロキシ化合物(V)として4,4’-ビフェノール93g(芳香族モノヒドロキシ化合物(III)としての2,6-キシレノールのモル数に対して4分の1モル量)を用いたこと以外は実施例5と同様にして、白色粉末357gを得た。
得られた白色粉末は、融点187~189℃であった。
なお、第1工程の反応混合物の塩素含有率は10.4重量%であった。
GPCにより、得られた白色粉末の組成を測定したところ、化合物(5)で表される芳芳香族ジホスフェート(I)が96.4面積%、化合物(6)で表されるヒドロキシフェニル基を有するリン化合物(II)が1.2面積%、化合物(7)で表される芳香族モノホスフェート(VI)が2.0面積%および化合物(10)で表される芳香族トリホスフェート(VII)が0.4面積%であった。
得られた結果を使用した原料と共に表1に示す。
一方、第2工程における芳香族ジヒドロキシ化合物(III)の使用量を調整しない場合には、反応スケールを大きくすると、ヒドロキシフェニル基を有するリン化合物(II)の生成量が増加する傾向にあることがわかる(例えば、比較例1と2との対比)。
樹脂として、変性PPE樹脂(日本ジーイープラスチックス社製、商品名:ノリル731)、PC/ABSアロイ樹脂(ダイセルポリマー株式会社製、商品名:ノバロイS-1500)およびABS樹脂(ダイセルポリマー株式会社製、商品名:セビアンV-500)、添加剤にドリップ防止剤としてフッ素樹脂(三井デュポンフロロケミカル株式会社製、商品名:テフロン(登録商標)6-J)を用いた。
表2~4に示す配合をミキサーで混合後、250~300℃に保持した押出機を通してコンパウンディングペレットを得た。得られたペレットを射出成形機にいれ、250~300℃で成形し、試験片を得た。
また、下記の耐久性試験として、恒温恒湿器または耐候光試験機で処理した後の試験片について、アイゾット衝撃強度およびメルトフローレートを測定した。
得られた結果を樹脂組成物の配合と共に表2~4に示す。
試験方法:UL-94に準拠(5検体の平均消炎時間)
試験片:厚さ1.6mm
評価:規定によるランク V-0、V-1およびV-2
(2)アイゾット衝撃強度
試験方法:ASTM D-256に準拠
試験片:厚さ3.2mm
単位:J/m
試験方法:JIS K7210、操作Aに準拠
温度:変性PPE樹脂275℃、PC/ABSアロイ樹脂230℃、ABS樹脂 200℃
荷重:変性PPE樹脂2.16kg、PC/ABSアロイ樹脂5kg、ABS樹脂5kg
単位:g/10分(min)
熱と荷重により、樹脂や難燃剤の分子結合が切れて分子量が低下すると、樹脂組成物の流動性が大きくなるので、これを測定することにより、樹脂組成物の安定性の目安とすることができる。
試験方法:ASTM D-648に準拠
試験片:厚さ6.4mm
荷重:曲げ応力1.8MPa
単位:℃
(5)曲げ強さ
試験方法:ASTM D-790に準拠
試験片:厚さ6.4mm
単位:MPa
(6)恒温恒湿器
試験機:タバイエスペック株式会社製、商品名:プラチナスレインボーPR-1G
試験槽温度:80℃
試験槽湿度:80%RH
6時間および24時間処理した試験片について、それぞれアイゾット衝撃強度およびメルトフローレートを測定した。表2~4中、それぞれレインボー6HR処理後およびレインボー24HR処理後と記載記載し、初期値に対する割合を維持率(%)として付記する。
試験機:スガ試験機株式会社製、商品名:デューパネルウェザーメーターDPWL-5
試験槽温度:60℃
照射波長:ピーク波長313nm(紫外線蛍光ランプ)
照射強度:2.0mW/cm2
100時間処理した試験片について、アイゾット衝撃強度を測定した。表2~4中、デューパネル100HR処理後と記載し、初期値に対する割合を維持率(%)として付記する。
表2~4に示した配合を用いて、実施例7~15と同様にして試験片を得、物性を測定した。
得られた結果を表2~4に示す。
一方、耐久性試験後のアイゾット衝撃強度およびメルトフローレートについては、両者の差は非常に大きく、その差は歴然としており、前者が耐久性試験前の物性の低下を抑制し、優れていることがわかる。
いる。
すなわち、本発明のリン系難燃剤組成物を含有する難燃性樹脂組成物の成形体は、アイゾット衝撃強度およびメルトフローレートに優れ、特に温度および湿度への耐久性に優れることがわかる。
Claims (8)
- 前記芳香族ジホスフェート化合物が、GPC測定で95面積%以上含まれる請求項1に記載のリン系難燃剤組成物。
- 前記芳香族ジホスフェート化合物が、GPC測定で0.01面積%以上0.9面積%以下の前記ヒドロキシフェニル基を有するリン化合物を含有する請求項1に記載のリン系難燃剤組成物。
- 前記芳香族ジホスフェート化合物と前記ヒドロキシフェニル基を有するリン化合物が、テトラキス(2,6-ジメチルフェニル)-m-フェニレン-ビスホスフェートとビス(2,6-ジメチルフェニル)-3-ヒドロキシフェニルホスフェート、テトラキス(2,6-ジメチルフェニル)-p-フェニレン-ビスホスフェートとビス(2,6-ジメチルフェニル)-4-ヒドロキシフェニルホスフェート、またはテトラキス(2,6-ジメチルフェニル)-4,4'-ジフェニレンビスホスフェートとビス(2,6-ジメチルフェニル)-4'-ヒドロキシフェニル-4-フェニルホスフェートの組み合わせである請求項1に記載のリン系難燃剤組成物。
- 前記芳香族ジホスフェート化合物と前記ヒドロキシフェニル基を有するリン化合物が、テトラキス(2,6-ジメチルフェニル)-m-フェニレン-ビスホスフェートとビス(2,6-ジメチルフェニル)-3-ヒドロキシフェニルホスフェートである請求項4に記載のリン系難燃剤組成物。
- ポリカーボネート系樹脂、ポリフェニレンエーテル系樹脂、ゴム変性スチレン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂およびエポキシ系樹脂から選択される1種以上の樹脂と、請求項1に記載のリン系難燃剤組成物とを含有することを特徴とする難燃性樹脂組成物。
- 前記難燃性樹脂組成物が、前記樹脂100重量部に対して、0.1~100重量部の割合で前記リン系難燃剤組成物を含有する請求項6に記載の難燃性樹脂組成物。
- 請求項6に記載の難燃性樹脂組成物からなることを特徴とする成形体。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/144,217 US20110263767A1 (en) | 2009-01-19 | 2009-12-17 | Phosphorus flame retardant, flame-retardant resin composition containing same, and molded body |
EP09838391.2A EP2380948B1 (en) | 2009-01-19 | 2009-12-17 | Method for preparing a phosphorus flame retardant composition |
JP2010546558A JP5700789B2 (ja) | 2009-01-19 | 2009-12-17 | リン系難燃剤組成物およびそれを含有する難燃性樹脂組成物、成形体 |
CN2009801548294A CN102282236A (zh) | 2009-01-19 | 2009-12-17 | 磷系阻燃剂组合物及含有其的阻燃性树脂组合物、成型体 |
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EP (1) | EP2380948B1 (ja) |
JP (1) | JP5700789B2 (ja) |
KR (1) | KR20110117126A (ja) |
CN (2) | CN104987531A (ja) |
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Cited By (6)
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JP2011190371A (ja) * | 2010-03-15 | 2011-09-29 | Asahi Kasei Chemicals Corp | 樹脂組成物 |
GB2487455A (en) * | 2010-12-30 | 2012-07-25 | Cheil Ind Inc | Flame retardant polyphosphonates and their use in polycarbonate resins |
WO2014171358A1 (ja) | 2013-04-15 | 2014-10-23 | 大八化学工業株式会社 | 難燃剤組成物ならびにそれを含有する難燃性樹脂組成物および成形体 |
KR101459123B1 (ko) * | 2010-12-30 | 2014-11-12 | 제일모직주식회사 | 폴리포스포네이트, 그의 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물 |
KR20200035845A (ko) | 2018-09-27 | 2020-04-06 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | 인 함유 경화제, 그 인 함유 경화제와 에폭시 수지를 함유하는 에폭시 수지 조성물, 및 그 경화물 |
WO2021256351A1 (ja) * | 2020-06-15 | 2021-12-23 | 日鉄ケミカル&マテリアル株式会社 | リン含有フェノール化合物、これを含む硬化性樹脂組成物、およびその硬化物 |
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CN102558225B (zh) * | 2011-12-12 | 2015-03-11 | 湖北犇星化工有限责任公司 | 一种芳香基磷酯高效阻燃剂及其合成方法 |
CN103483621B (zh) * | 2012-06-08 | 2017-09-12 | 大八化学工业株式会社 | 树脂用阻燃剂及包含其的阻燃性树脂组合物 |
CN103570759B (zh) * | 2012-07-26 | 2015-11-18 | 中国石油天然气股份有限公司 | 间苯二酚双(二-2,6-二甲基苯基磷酸酯)的连续化碱洗方法 |
CN105859769B (zh) * | 2015-01-23 | 2018-11-09 | 浙江新安化工集团股份有限公司 | 一种减少废水产生的磷酸酯阻燃剂后处理装置及方法 |
CN106995535A (zh) * | 2017-04-18 | 2017-08-01 | 三峡大学 | 一种含环三磷腈的双磷酸苯酯磷氮协同阻燃剂的制备方法及其应用 |
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- 2009-12-17 EP EP09838391.2A patent/EP2380948B1/en active Active
- 2009-12-17 US US13/144,217 patent/US20110263767A1/en not_active Abandoned
- 2009-12-17 CN CN201510342519.2A patent/CN104987531A/zh active Pending
- 2009-12-17 JP JP2010546558A patent/JP5700789B2/ja active Active
- 2009-12-17 WO PCT/JP2009/071037 patent/WO2010082426A1/ja active Application Filing
- 2009-12-17 KR KR1020117017840A patent/KR20110117126A/ko not_active Application Discontinuation
- 2009-12-17 CN CN2009801548294A patent/CN102282236A/zh active Pending
- 2009-12-23 TW TW098144467A patent/TW201030131A/zh unknown
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JPH051079A (ja) | 1991-04-16 | 1993-01-08 | Daihachi Chem Ind Co Ltd | 芳香族ジホスフエートの製造方法と用途 |
JPH0987290A (ja) | 1995-09-22 | 1997-03-31 | Daihachi Chem Ind Co Ltd | 芳香族ホスフェート類の粉末化方法 |
JP2001226386A (ja) * | 2000-02-15 | 2001-08-21 | Daihachi Chemical Industry Co Ltd | リン酸エステルの精製方法 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011190371A (ja) * | 2010-03-15 | 2011-09-29 | Asahi Kasei Chemicals Corp | 樹脂組成物 |
GB2487455A (en) * | 2010-12-30 | 2012-07-25 | Cheil Ind Inc | Flame retardant polyphosphonates and their use in polycarbonate resins |
KR101459123B1 (ko) * | 2010-12-30 | 2014-11-12 | 제일모직주식회사 | 폴리포스포네이트, 그의 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물 |
WO2014171358A1 (ja) | 2013-04-15 | 2014-10-23 | 大八化学工業株式会社 | 難燃剤組成物ならびにそれを含有する難燃性樹脂組成物および成形体 |
KR20150143520A (ko) | 2013-04-15 | 2015-12-23 | 다이하치 카가쿠 고교 가부시키가이샤 | 난연제 조성물 및 그것을 함유하는 난연성 수지 조성물 및 성형체 |
JPWO2014171358A1 (ja) * | 2013-04-15 | 2017-02-23 | 大八化学工業株式会社 | 難燃剤組成物ならびにそれを含有する難燃性樹脂組成物および成形体 |
KR20200035845A (ko) | 2018-09-27 | 2020-04-06 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | 인 함유 경화제, 그 인 함유 경화제와 에폭시 수지를 함유하는 에폭시 수지 조성물, 및 그 경화물 |
WO2021256351A1 (ja) * | 2020-06-15 | 2021-12-23 | 日鉄ケミカル&マテリアル株式会社 | リン含有フェノール化合物、これを含む硬化性樹脂組成物、およびその硬化物 |
Also Published As
Publication number | Publication date |
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US20110263767A1 (en) | 2011-10-27 |
EP2380948B1 (en) | 2019-07-03 |
CN102282236A (zh) | 2011-12-14 |
EP2380948A1 (en) | 2011-10-26 |
CN104987531A (zh) | 2015-10-21 |
EP2380948A4 (en) | 2013-11-13 |
JPWO2010082426A1 (ja) | 2012-07-05 |
JP5700789B2 (ja) | 2015-04-15 |
KR20110117126A (ko) | 2011-10-26 |
TW201030131A (en) | 2010-08-16 |
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