JP2018065758A - Compound, and flame retardant and flame-retardant resin composition which employ that compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel compound that generates little carbon monoxide harmful for a human body during combustion, e.g., in a fire, and has excellent flame retardance; and a flame retardant and a flame-retardant resin composition which employ the compound.SOLUTION: A compound represented by any of the general formulas (1) to (4) in the figure is employed as a flame retardant. In the formulas (1) and (2), each independently, p is a number from 0.3 to 2, R is an integer from 1 to 6, and A represents a metal atom. In the formulas (3) and (4), each independently, q is an integer from 0 to 2, and B represents a hydrogen atom or amine compound.SELECTED DRAWING: None

Description

  The present invention relates to a compound, a flame retardant using the compound, and a flame retardant resin composition, and more specifically, the occurrence of carbon monoxide harmful to the human body at the time of combustion such as a fire is small, and the flame retardancy is excellent. The present invention relates to a flame retardant and a flame retardant resin composition using the compound.

  Thermoplastic resins such as polyester resins, polyolefin resins, vinyl resins, polycarbonate resins, acrylic resins, styrene resins, polyamide resins, polyphenylene oxide resins, polyphenylene sulfide resins are excellent chemical and mechanical Because of its physical properties, it is widely used for building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys, etc., due to its chemical and mechanical properties. However, many thermoplastic resins are flammable materials, and flame retardant is indispensable depending on applications.

  In order to impart flame retardancy to these thermoplastic resins, it is represented by halogen-based flame retardants, inorganic phosphorous flame retardants represented by polyphosphoric flame retardants such as red phosphorus and ammonium polyphosphate, and triaryl phosphate ester compounds. It is widely known to use organic phosphorus-based flame retardants, metal hydroxides and flame retardant assistants such as antimony oxide and melamine compounds alone or in combination.

For example, Patent Document 1 describes a dialkylphosphinic acid metal salt as a flame retardant for thermoplastic resins, particularly for polyester resins, styrene resins, or polyamide resins.
Patent Document 2 describes polyphosphonates as flame retardants for polyester resins, and Patent Document 3 discloses difficulty in using nitrogen compounds such as melamine phosphate and ammonium polyphosphate in combination with bicyclic phosphate compounds. The flame retardant is described as a flame retardant for polyolefin resin, vinyl resin, polycarbonate resin, acrylic resin, or polyamide resin. Patent Documents 4 and 5 describe that organic sulfonates are polycarbonate-based. Patent Document 6 describes a sulfide salt as a flame retardant for polycarbonate resin, and Patent Documents 7 and 8 describe a magnesium hydroxide as a flame retardant for polyamide resin. Patent Documents 9 and 10 describe melamine cyanurate as polyamide. Patent Document 11 describes a flame retardant using a combination of a phosphonate compound and ammonium polyphosphate as a flame retardant for polyphenylene oxide, and Patent Document 12 describes a phosphate compound and antimony trioxide. Is described as a flame retardant for polyphenylene oxide.

Special table 2001-525327 gazette U.S. Pat. No. 3,719,727 Japanese Examined Patent Publication No. 4-57707 Japanese Patent Laid-Open No. 50-98539 JP 50-98540 A Japanese Patent Publication No. 01-22304 JP 54-83952 A JP 54-131645 A JP-A-53-31759 JP 54-91558 A JP 52-86449 A JP 49-32947 A

In general, it is presumed that incombustibility is incomplete combustion, and depending on the incombustibility mechanism, there is a possibility that dilution of oxygen (O ₂ ) concentration is caused by release of a large amount of harmful gas such as carbon monoxide. While flame retardancy is important for preventing a fire, development of a flame retardant that generates as little carbon monoxide as possible during combustion is desired when an actual fire is assumed.

The flame retardants of Patent Documents 1 to 12 use incomplete combustion of materials as a flame retardant mechanism, leading to O ₂ dilution due to the generation of a large amount of gas and generation of harmful CO, accompanied by the generation of a large amount of smoke and soot. . In other words, while it becomes flame retardant, CO which becomes a problem after a fire is on the rise, it has high flame retardancy and is a material that reduces the generation of smoke, CO and soot after combustion occurs Is expected.

  Accordingly, an object of the present invention is to provide a compound that generates little carbon monoxide harmful to the human body during combustion such as in a fire and has excellent flame retardancy, a flame retardant using the compound, and a flame retardant resin composition There is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that when a specific phosphonic acid compound is used as a flame retardant, the generation of carbon monoxide is small, and the present invention has been completed. It was.

式（１）および（２）中、各々独立に、ｐは０．３〜２の数であり、Ｒは１〜６の整数であり、Ａは金属原子を表す。
式（３）および（４）中、各々独立に、ｑは０〜２の整数であり、Ｂはアミン化合物を表す。 The present invention provides a compound represented by any one of the following general formulas (1) to (4) and a flame retardant containing the compound.

In formulas (1) and (2), each independently, p is a number from 0.3 to 2, R is an integer from 1 to 6, and A represents a metal atom.
In formulas (3) and (4), q independently represents an integer of 0 to 2, and B represents an amine compound.

  Moreover, this invention provides the flame-retardant resin composition containing the said flame retardant 1-50 mass parts with respect to 100 mass parts of thermoplastic resins.

  According to the present invention, when used as a flame retardant, a compound having less carbon monoxide and excellent in flame retardancy is provided.

1 shows the compound No. used in Example 1-1. It is a figure which shows ¹ H-NMR of 3-1. 2 shows the compound No. 1 used in Example 1-1. It is a figure which shows ¹³ C-NMR of 3-1. 3 shows the compound No. used in Example 1-1. It is a figure which shows ³¹ P-NMR of 3-1. 4 shows the compound No. used in Example 1-3. It is a figure which shows ¹ H-NMR of 4-1. FIG. 5 shows the compound No. used in Example 1-3. It is a figure which shows ¹³ C-NMR of 4-1. 6 shows the compound No. used in Example 1-3. It is a figure which shows ³¹ P-NMR of 4-1. FIG. 7 is a graph showing the relationship between the combustion time and the amount of carbon monoxide generated when the resin compositions of Example 2-5 and Comparative Example 1-2 were burned.

  Hereinafter, the present invention will be described in detail. The compound of the present invention is a novel condensed phosphonic acid compound represented by any one of the general formulas (1) to (4). In the general formulas (1) and (2), examples of the metal atom represented by A include metal atoms belonging to Group 1, Group 4, Group 13, Group 2, Group 12 and the like of the periodic table. It is done. Examples of the metal belonging to Group 1 of the periodic table include sodium and potassium. Examples of the metal belonging to Group 2 of the periodic table include magnesium and calcium. Examples of the metal belonging to Group 4 of the periodic table include titanium and zirconium. Examples of the metal belonging to Group 12 of the periodic table include zinc. Examples of the metal belonging to Group 13 of the periodic table include aluminum. Among these, at least one selected from the group consisting of calcium, zinc and aluminum is preferable from the viewpoint of water resistance.

  When q is 0, the compounds represented by the general formulas (3) and (4) are compound Nos. Described later. 3-1. 4-1. When q is 1, the compound No. in the compound represented by the general formula (3) is shown. The structure corresponding to 3-1 or the compound No. represented by the general formula (4) One OH group in the structure corresponding to 4-1 and one electron pair of N atom in the amine compound represented by B exist in a bonded state. When q is 2, compound no. The structure or compound no. Two OH groups in the structure corresponding to 4-1 are present in a state of being bonded to an electron pair of one N atom of each of the amine compounds represented by two Bs.

  Examples of the amine compound represented by B include aliphatic amines and heterocyclic amines. Examples of the aliphatic amine include ethylenediamine, diethylenetriamine, and triethylenetetramine. Examples of the heterocyclic amine include melamine, piperazine, hexamethylenetetramine and the like. Among these, at least one selected from the group consisting of melamine, piperazine, ethylenediamine, diethylenetriamine, and triethylenetetramine is preferable from the viewpoint of heat resistance.

  Examples of the compound represented by the general formula (1) of the present invention include the following compound No. 1-1-No. 1-11 etc. are mentioned.

  Examples of the compound represented by the general formula (2) include the following compound No. 2-1. 2-11 and the like.

  Examples of the compound represented by the general formula (3) include the following compound No. 3-1. 3-11 etc. are mentioned.

  Examples of the compound represented by the general formula (4) include the following compound No. 4-1. 4-11 and the like.

Any of the compounds represented by the general formulas (1) to (4) can be produced by a conventionally known method. For example, in the case of the compound represented by the general formula (1), first, according to the method of Example 1-1 described later, the compound No. 1 which is a phosphonic acid compound is used. 3-1. Next, the obtained compound No. The compound represented by general formula (1) can be produced by reacting 3-1 with a reagent capable of supplying a metal atom corresponding to A in general formula (1).
In the case of the compound represented by the general formula (2), first, according to the method of Example 1-3 described later, a compound No. 1 which is a phosphonic acid compound. 4-1 is produced. Next, the obtained compound No. The compound represented by general formula (2) can be produced by reacting 4-1 with a reagent capable of supplying a metal atom corresponding to A in general formula (2).
In the case of the compound represented by the general formula (3), first, according to the method of Example 1-1 described later, the compound No. 1 which is a phosphonic acid compound is used. 3-1. Next, the obtained compound No. A compound represented by the general formula (3) can be produced by binding a solution containing an amine compound corresponding to B in the general formula (3) to 3-1.
In the case of the compound represented by the general formula (4), first, according to the method of Example 1-3 described later, a compound No. 1 which is a phosphonic acid compound. 4-1 is produced. Next, the obtained compound No. The compound represented by General formula (4) can be manufactured by combining the solution containing the amine compound corresponding to B in General formula (4) to 4-1.

  The compound represented by any one of the general formulas (1) to (4) described above is preferably used as a flame retardant, chelating agent, scale inhibitor, heat resistance improver, dispersant, stabilizer for resin. , Nucleating agent, clearing agent, filler-filled plastic additive, coating base agent, organic synthesis catalyst, rust preventive agent, metal oxide surface treating agent, and the like.

  The flame retardant of the present invention contains at least one compound represented by the general formulas (1) to (4) (hereinafter also referred to as “phosphonic acid compound”). The content of the phosphonic acid compound in the flame retardant of the present invention is preferably 1 to 100% by mass and more preferably 50 to 100% by mass in the flame retardant of the present invention. By setting the content of the phosphonic acid compound to 50% by mass or more, the flame retardant of the present invention has little generation of carbon monoxide and is excellent in flame retardancy.

  In the flame retardant of the present invention, other flame retardants may be used in addition to the phosphonic acid compound as long as the effects of the present invention are not impaired. Examples of such flame retardants include halogen flame retardants, red phosphorus, melamine phosphate, ammonium polyphosphate, melamine polyphosphate, melamine pyrophosphate, piperazine polyphosphate, piperazine pyrophosphate, guanidine phosphate, and (condensed) phosphorus. Examples thereof include phosphorus flame retardants such as acid ester compounds and phosphazene compounds, nitrogen flame retardants such as melamine cyanurate, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, phosphinates and diphosphinates.

  The flame retardant of the present invention is used as a flame retardant for various synthetic resins, particularly for thermoplastic resins, specifically, polyester resins, polyolefin resins, vinyl resins, polycarbonate resins, acrylic resins, styrene resins. It can be preferably used as a flame retardant for at least one selected from the group consisting of resins, polyamide resins, polyphenylene oxide resins and polyphenylene sulfide resins.

  The flame retardant resin composition of the present invention contains 1 to 50 parts by mass of the flame retardant of the present invention with respect to 100 parts by mass of the thermoplastic resin. In the flame retardant resin composition of the present invention, the flame retardancy is a property that the substance is difficult to ignite, and that the rate is very slow even after ignition and combustion continues, and then self-extinguishes. It means that it preferably has at least a V-2 rank among the combustion ranks according to the UL-94V standard described in the examples.

  In the flame retardant resin composition of the present invention, the content of the flame retardant of the present invention is 1 to 50 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 30 parts by mass. In the flame retardant resin composition of the present invention, the flame retardancy of the resin is improved by setting the flame retardant of the present invention to 1 part by mass or more. Moreover, the workability of resin is not impaired by setting the flame retardant of this invention to 50 mass parts or less.

  Examples of the thermoplastic resin include polyester resins, polyolefin resins, vinyl resins, polycarbonate resins, acrylic resins, styrene resins, polyamide resins, polyphenylene oxide resins, polyphenylene sulfide resins, and the like. . These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be alloyed.

  The thermoplastic resin has a melt flow rate (MFR) of 2.0 to 80 g / 10 min at a load of 2.16 kg and a temperature of 230 ° C. measured in accordance with JIS K7210 from the viewpoint of workability and flame retardancy. A certain thing is preferable and the thing of 8.0-60 g / 10min is more preferable.

  As the polyester resin, a divalent acid such as terephthalic acid as an acid component, or a derivative thereof having an ester forming ability, a glycol having 2 to 10 carbon atoms as a glycol component, other divalent alcohol, or The saturated polyester resin obtained using those derivatives etc. which have ester formation ability are mentioned. Among these, a polyalkylene terephthalate resin is preferable in that it has an excellent balance of processability, mechanical properties, electrical properties, heat resistance, and the like. Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin.

  Examples of the polyolefin resin include polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, high impact copolymer polypropylene, and isotactic. Polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, maleic anhydride modified polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly Α-olefin polymer such as -4-methyl-1-pentene, ethylene / propylene block or lander Copolymer, ethylene - methyl methacrylate copolymer, ethylene - alpha-olefin copolymers such as vinyl acetate copolymer.

  Examples of the vinyl resin include vinyl monomers (for example, vinyl esters such as vinyl acetate; chlorine-containing vinyl monomers (for example, vinyl chloride); vinyl ketones; vinyl ethers; vinylamines such as N-vinylcarbazole). And the like, or copolymers with other copolymerizable monomers. Derivatives of the vinyl resins (for example, polyvinyl acetals such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, and ethylene-vinyl acetate copolymers) can also be used.

Examples of the polycarbonate resin include those obtained by reacting one or more bisphenols with phosgene or a carbonic acid diester, or those obtained by reacting one or more bisphenols with a diphenyl carbonate by a transesterification method. Can be mentioned. Examples of the bisphenols include hydroquinone, 4,4-dihydroxyphenyl, bis- (4-hydroxyphenyl) -alkane, bis- (4-hydroxyphenyl) -cycloalkane, and bis- (4-hydroxyphenyl) -sulfide. , Bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -ketone, bis- (4-hydroxyphenyl) -sulfone, bisphenolfluorene or their alkyl-substituted, aryl-substituted, halogen-substituted Etc. These are used singly or in combination of two or more.
As the polycarbonate-based resin, a so-called polymer alloy obtained by mixing polycarbonate and another resin can also be used. Examples of such polymer alloys include polycarbonate / ABS resin, polycarbonate / AS resin, polycarbonate / rubber polymer compound, polycarbonate / ABS resin / rubber polymer compound, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, Examples include polycarbonate / ASA resin and polycarbonate / AES resin. The ratio of the polycarbonate contained in these polymer alloys is preferably 50 to 98% by mass in the polymer alloy.

  Examples of the acrylic resin include polymers mainly composed of (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. A homopolymer of (meth) acrylic acid ester may be used, or a copolymer of 50% by weight or more of methacrylic acid ester and 50% by weight or less of other monomers may be used. As monomers other than (meth) acrylic acid esters, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; alkenyl cyanide compounds such as acrylonitrile and methacrylonitrile; unsaturateds such as acrylic acid and methacrylic acid Carboxylic acid; maleic anhydride; monofunctional monomer such as N-substituted maleimide; polyunsaturated carboxylic acid ester of polyhydric alcohol such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate; acrylic acid Alkenyl esters of unsaturated carboxylic acids such as allyl, allyl methacrylate, allyl cinnamate; polyalkenyl ethers of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate Ether; polyfunctional monomers such as aromatic polyalkenyl compounds such as divinylbenzene and the like.

  Examples of the styrenic resin include styrene monomers (styrene, vinyltoluene, etc.) or copolymers; styrene monomers and vinyl monomers [(meth) acrylic monomers (for example, ( (Meth) acrylonitrile, (meth) acrylic acid ester, (meth) acrylic acid etc.), α, β-monoolefinic unsaturated carboxylic acid or acid anhydride or ester etc. such as maleic anhydride, etc.]; styrene Examples thereof include a graft copolymer and a styrene block copolymer.

Examples of the polyamide resin include aliphatic polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12, and alicyclic diamines such as bis (aminocyclohexyl) C _1-3 alkanes. And alicyclic polyamides obtained from aliphatic dicarboxylic acids such as C _8-14 alkanedicarboxylic acids; aromatic dicarboxylic acids (eg terephthalic acid and / or isophthalic acid) and aliphatic diamines (eg hexamethylenediamine, nona And polyamides obtained from aromatic and aliphatic dicarboxylic acids (eg, terephthalic acid and adipic acid) and aliphatic diamines (eg, hexamethylene diamine).

Examples of the polyphenylene oxide resin include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,5-dimethyl-1,4-phenylene) oxide, poly (2,5-diethyl-1, Poly (mono, di or tri C _1-6 alkyl-phenylene) oxide such as 4-phenylene) oxide, poly (mono or di C _6-20 aryl-phenylene) oxide, poly (mono C _1-6 alkyl-mono C) _6-20 aryl-phenylene) oxide and other homopolymers, random copolymers having 2,6-dimethyl-1,4-phenylene oxide units and 2,3,6-trimethyl-1,4-phenylene oxide units. Polymer), benzene formaldehyde resin (phenol resin, etc.) and alkylbenzene formaldehyde resin, A modified polyphenylene oxide copolymer composed of an alkylphenol-modified benzene formaldehyde resin block obtained by reacting alkylphenol such as ruthenium and a polyphenylene oxide block as a main structure, a polyphenylene oxide or a copolymer thereof and a styrenic polymer and And / or a modified graft copolymer grafted with an unsaturated carboxylic acid or anhydride ((meth) acrylic acid, maleic anhydride, etc.).

Examples of the polyphenylene sulfide-based resin include homopolymers and copolymers having a phenylene sulfide skeleton- (Ar-S)-[wherein Ar represents a phenylene group]. As the phenylene group (-Ar-), Is, for example, a p-, m-, or o-phenylene group, a substituted phenylene group (for example, an alkylphenylene group having a substituent such as a C _1-6 alkyl group, or an arylphenylene having a substituent such as a phenyl group) group), - wherein, Ar is a phenylene group, ^{a 1} is a direct bond, O, CO, or an SO _2] ^Ar-a 1 -Ar-, or the like.

  The flame retardant resin composition of the present invention may further contain glass fibers and / or fluorinated carbon-based polymers. Glass fiber and fluorinated carbon-based polymer function as a flame retardant aid.

  The glass fiber is not particularly limited in type, and any of E glass, C glass, S glass, D glass and the like can be used, and the form is not particularly limited, and chopped strand, roving, yarn, glass wool, etc. Any glass fiber can be used, but chopped strands are preferred from the viewpoint of workability. When chopped strands are used, the glass fiber has a fiber length (cut length) of 0.5 to 10 mm, a fiber diameter (filament diameter) of 8 to 20 μm, particularly a fiber length of 2 to 5 mm, and a fiber diameter of 10 to 15 μm. It is preferable to use it.

  In the flame retardant resin composition of the present invention, the glass fiber content is preferably 10 to 120 parts by mass, more preferably 30 to 100 parts by mass, and still more preferably 100 parts by mass of the thermoplastic resin. 40 to 80 parts by mass. By setting the glass fiber content to 10 parts by mass or more, the effect of improving the mechanical properties of the resin by the glass fiber can be seen. On the other hand, by setting the glass fiber content to 120 parts by mass or less, the mechanical properties of the resin are improved without reducing the workability and flame retardancy.

In the flame-retardant resin composition of the present invention, a lubricant may be blended as necessary within a range not impairing the effects of the present invention. Such lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, low molecular weight polyethylene and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids. ; Fatty acid amide type lubricants such as fatty acid amides and bis fatty acid amides; Ester type lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes) Metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester lubricant, silicone oil, mineral And the like. Two or more lubricants may be used.
When the lubricant is contained, the content is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

  If necessary, the flame retardant resin composition of the present invention may be blended with a phenol-based antioxidant, a phosphorus-based antioxidant, or the like. These components may be blended in advance with the flame-retardant resin composition of the present invention, or may be blended with the thermoplastic resin when blended with the thermoplastic resin. It is preferable to stabilize the thermoplastic resin by blending these.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Ditertiarybutyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, thiodiethyleneglycol Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] And ndecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. The amount of these phenolic antioxidants used is preferably 0.001 to 5% by mass, and 0.05 to 3% by mass in the flame retardant resin composition when blended with a thermoplastic resin. More preferably.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. The amount of these phosphorus-based antioxidants used is preferably 0.001 to 5% by mass in the flame-retardant resin composition when blended with the thermoplastic resin, and 0.05 to 3% by mass. More preferably.

  The flame retardant resin composition of the present invention may further contain a crystal nucleating agent as an optional component as long as the effects of the present invention are not impaired. As the crystal nucleating agent, those generally used as a polymer crystal nucleating agent can be used as appropriate. In the present invention, either an inorganic crystal nucleating agent or an organic crystal nucleating agent can be used.

  Specific examples of the inorganic crystal nucleating agent include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, Mention may be made of metal salts such as neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.

  Specific examples of the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, and oxalic acid. Calcium, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate Organic carboxylic acid metal salts such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearamide , Carboxylic acid amides such as ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis (4 , 6-di-t-butylphenyl) phosphate, metal salts of phosphorus compounds, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium It can be.

  In the flame-retardant resin composition of the present invention, a plasticizer may be blended as an optional component as long as the effects of the present invention are not impaired. As the plasticizer, those generally used as polymer plasticizers can be used as appropriate. For example, polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers and epoxies. Examples thereof include plasticizers.

  In addition, in the flame-retardant resin composition of the present invention, additives that are usually used in thermoplastic resins as necessary, for example, crosslinking agents, antistatic agents, metal soaps, spotting agents, antifogging agents, plates Anti-out agents, surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids other than acrylic processing aids, etc. It can mix | blend in the range which is not impaired.

  In order to obtain the flame retardant resin composition of the present invention, the thermoplastic resin which is an essential component and the flame retardant of the present invention, if necessary, glass fiber and / or fluorinated carbon-based polymer, and further if necessary Other arbitrary components may be mixed, and various mixers can be used for mixing. You may heat at the time of mixing. Examples of the mixer that can be used include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer.

  By molding the flame retardant resin composition of the present invention, a molded product having excellent flame retardancy can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, etc., and molded products having various shapes such as resin plates, sheets, films, and irregular shaped products. Can be manufactured.

  The flame-retardant resin composition of the present invention can be used for housings (frames, housings, covers, exteriors) and parts of automobiles, machines, electrical / electronic devices, OA devices, automotive interior / exterior materials, and the like.

  The flame-retardant resin composition of the present invention and the molded product thereof are electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical treatment, coal, petroleum, rubber, leather, automobile, precision equipment, wood. It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing and musical instruments. More specifically, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc. Office work, office equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other household appliances, TV, VTR, video camera, radio cassette, tape recorder, mini-disc, CD player, speaker, Electrical and electronic parts such as liquid crystal displays and other AV equipment, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, watches, etc. And housings (frames, housings, covers, exteriors) and parts for communication equipment and OA equipment , Used in applications in automotive exterior material.

  Further, the flame-retardant resin composition and molded product thereof according to the present invention include a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover. , Mattress cover, air bag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring, corner wall, carpet, wallpaper, wall covering material, exterior material , Interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, fence materials, frames and repetitive shapes, window and door shapes, slabs, siding, terraces, balconies, soundproofing plates, heat insulating plates, windows Materials such as automobiles, hybrid cars, electric cars, vehicles, ships, aircraft, buildings, housing and building materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic boards, carpets, entrances Tsu door, seat, bucket, hose, container, glasses, bags, cases, goggles, skis, rackets, tents, household items such as musical instruments, used in sporting goods, various applications, such as.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples. In addition, the unit of the compounding quantity in a table | surface shall be a mass part.

[Synthesis of condensed phosphonic acid]
[Example 1-1] Compound No. 1 Synthesis of 3-3 <Step 1> Compound No. Synthesis of 3-1 10.00 g (5.71 × 10 ⁻² mol) of α-αdichloroparaxylene and tributyl phosphite were added to a four-necked flask equipped with a three-one motor equipped with a semicircular stirring blade. 42.89 g (1.71 × 10 ⁻¹ mol) was added, and the temperature was raised to 160 ° C. After the reaction for 6 hours, vacuum distillation was performed at 160 ° C. and 1 KPa for 5 hours. 115.55 g (6.86 × 10 ⁻¹ mole) of 48% HBr aqueous solution was added, and the reaction was allowed to proceed at 100 ° C. for 12 hours. A white solid appeared in the system as the reaction proceeded. After completion of the reaction, the mixture was filtered, washed with water and hexane, and then calcined at 250 ° C. in an Ar atmosphere for 2 hours. 13.32 g (yield 94.0%) of 3-1 was obtained.
The obtained Compound No. Identification of 3-1 was performed by ¹ H-NMR, ¹³ C-NMR, and ³¹ P-NMR (measurement apparatus: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). The identification results by NMR are shown in the following <Identification results> and FIGS.

<Identification results>
¹ H-NMR (D ₂ O, 400 MHz): δ (ppm) 7.36-7.29 (m, 4H, ph), 3.40-3.35 (q, 4H, —CH ₂ —)
¹³ C-NMR (D ₂ O, 400 MHz): δ (ppm): 132.01, 131.58, 130.44, 128.03, 127.95, 126.42, 126.34, 33.71, 32 .44, 31.18, 29.91
³¹ P-NMR (D ₂ O, 400 MHz): δ (ppm): 13.73, 13.68, 13.65, 13.61, 13.57, 13.53, 13.50

<Step 2> Compound No. Synthesis of 3-3 Compound No. 1 obtained in Step 1 3-1 g (2.02 × 10 ⁻² mol) of 3-1 was added to a slurry solution of 9.32 g (4.04 × 10 ⁻² mol) of melamine and 100 g of water and stirred at 100 ° C. for 5 hours. Thereafter, the solid was filtered off and washed with pure water. It was dried at 100 ° C. for 3 hours in a vacuum drier, and the compound no. Compound No. 1 which is a melamine salt of 3-1. 8.96 g (yield 95.3%) of 3-3 was obtained. The obtained Compound No. 3-3 was identified by ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR (measurement apparatus: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). In addition to the identification results similar to those of 3-1, compound no. Compound No. 1 having a structure in which 3-1 and melamine are bound in a ratio of 1: 2 (the former: the latter). 3-3 was identified.

[Example 1-2] Compound No. 1 Synthesis of 3-4 Compound No. 1 obtained in Step 1 of Example 1-1. 3-1 5.00g of (2.02 × ^{10 -2} mоl), added with piperazine 1.74g (2.02 × ¹⁰ -2 mol) in an aqueous solution of water 100 g, and stirred for 5 hours at 100 ° C.. Thereafter, after concentration, the solid was separated by filtration and washed with pure water. It was dried at 100 ° C. for 3 hours in a vacuum dryer, Compound No. 1 which is a piperazine salt of 3-1. 5.93 g (yield 88.1%) of 3-4 was obtained. The obtained Compound No. 3-4 was identified by ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR (measurement apparatus: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). In addition to the identification results similar to those of 3-1, compound no. Compound No. 1 having a structure in which 3-1 and piperazine are combined at a ratio of 1: 1 (the former: the latter). 3-4 was identified.

[Example 1-3] Compound No. 1 Synthesis of 4-4 <Step 1> Compound No. Synthesis of 4-1 9.94 g (2.10 × 10 ^{−2) of} 1,2,4,5-tetrakisbromomethylbenzene was added to a 200 ml five-necked flask equipped with a three-one motor equipped with a half-moon shaped stirring blade. mol) and 26.28 g (1.05 × 10 ⁻¹ mol) of tributyl phosphite were added, and the temperature was raised to 130 ° C. After the reaction for 6 hours, vacuum distillation was performed at 160 ° C. and 1 PKa for 5 hours to remove excess phosphite. Thereafter, 70.96 g (4.20 × 10 ⁻¹ mole) of 48% HBr aqueous solution was added, and the reaction was allowed to proceed at 100 ° C. for 8 hours. After completion of the reaction, the mixture was filtered, washed with water and hexane, and then calcined at 250 ° C. for 2 hours in an Ar atmosphere. As a result, 7.82 g (yield: 89.1%) of 4-1 was obtained. The obtained Compound No. Identification of 4-1 was performed with ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR measuring devices (AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). The identification results by NMR are shown in the following <Identification results> and FIGS.

<Identification results>
¹ H-NMR (D ₂ O, 400 MHz): δ (ppm) 7.17 (s, 4H, ph) 3.38-3.34 (t, 4H, —CH ₂ —)
¹³ C-NMR (D ₂ O, 400 MHz): δ (ppm) 134.53, 132.91, 130.61, 32.23, 30.99
³¹ P-NMR (D ₂ O, 400 MHz): δ (ppm) 13.46

<Step 2> Compound No. Synthesis of 4-4 Compound No. obtained in Step 1 4-1 g (1.20 × 10 ⁻² mol) of 4-1 was added to an aqueous solution of 1.94 g (2.39 × 10 ⁻² mol) of piperazine and 100 g of water, followed by stirring at 100 ° C. for 5 hours. Thereafter, the solid was filtered off and washed with pure water. It was dried at 100 ° C. for 3 hours in a vacuum drier, and the compound no. Compound No. 4 which is a piperazine salt of 4-1; 6.73 g (yield 95.3%) of 4-4 was obtained. The obtained Compound No. 4-4 was identified by ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR (measurement apparatus: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). In addition to the identification results similar to those in Example 4-1, compound no. Compound No. 4-1 having a structure in which 4-1 and piperazine are combined at a ratio of 1: 2 (the former: the latter). 4-4 was identified.

[Examples 2-1 to 2-6 and Comparative Examples 1-1 and 1-2] Production and Evaluation of Flame Retardant Resin Composition The components shown in Table 1 below were blended to give a flame retardant resin composition. (Hereinafter referred to as “resin composition”). Details of each component described in Table 1 are as shown in Table 2. The obtained resin composition was extruded with an extruder (Ikegai Co., Ltd .: mold temperature 260 ° C.) to produce pellets. Using the obtained pellets, measurement of carbon monoxide generation amount and evaluation of flame retardance were performed as described below.

<Measurement of carbon monoxide generation>
The pellets obtained above were injection-molded (manufactured by Nissei Plastic Industry Co., Ltd., cylinder temperature 260 ° C., mold temperature 50 ° C.) to obtain test pieces having dimensions of 100 mm × 100 mm × 1.6 mm. The obtained test piece was tested under a radiant heat condition of 50 kW / m ² in accordance with ISO 5660 using a cone calorimeter (manufactured by Toyo Seiki Seisakusho: CONE III). The maximum amount of carbon monoxide (ppm) at that time is shown in Table 1. About Example 2-5 and Comparative Example 1-2, FIG. 7 shows the relationship between the combustion time and the amount of carbon monoxide generated when the resin composition is burned.

<Evaluation of flame retardancy>
The pellets obtained above were injection-molded (manufactured by Nissei Plastic Industry Co., Ltd., cylinder temperature 260 ° C., mold temperature 50 ° C.) to obtain test pieces having dimensions 127 mm × 12.7 mm × 1.6 mm. The obtained test piece was tested according to the flame retardancy standard UL-94V (underwriters laboratories standard). In the evaluation of flame retardancy, the flame retardancy of V-0 is the best, and the flame retardancy is inferior in the order of V-1 and V-2. When V-2 could not be achieved, it was determined as NR (Not Rating). The obtained results are shown in Table 1.

As is clear from the results in Table 1, the flame retardant resin composition containing the compound of the present invention as a flame retardant is not only excellent in flame retardancy but also has a small maximum amount of carbon monoxide generated. On the other hand, the flame-retardant resin composition not containing the compound of the present invention has not only insufficient flame retardancy but also a large maximum amount of carbon monoxide generated.
If the maximum amount of carbon monoxide generated is small, there is an advantage that in the event of a fire, the risk of sucking carbon monoxide that is harmful to the human body in a short time is reduced.
Further, from FIG. 7, the flame retardant resin composition of Example 2-5 has not only a small maximum amount of carbon monoxide generated, but also a small total amount of carbon monoxide generated. In contrast, the flame retardant resin composition of Comparative 1-2 has not only a large maximum amount of carbon monoxide generated, but also a large total amount of carbon monoxide generated.
If the total amount of carbon monoxide generated is small, there is an advantage that in the event of a fire, the risk of suffocation due to dilution of oxygen associated with the generation of harmful gases such as carbon monoxide is reduced.
From the above, it is clear that the compound of the present invention is excellent as a flame retardant.

Claims (8)

A compound represented by any one of the following general formulas (1) to (4).

In formulas (1) and (2), each independently, p is a number from 0.3 to 2, R is an integer from 1 to 6, and A represents a metal atom.
In formulas (3) and (4), q is independently an integer of 0 to 2, and B represents a hydrogen atom or an amine compound.   The compound according to claim 1, wherein the metal atom represented by A is at least one selected from the group consisting of sodium, potassium, titanium, zirconium and aluminum.   The compound according to claim 1, wherein the amine compound represented by B is at least one selected from the group consisting of melamine, piperazine, ethylenediamine, diethylenetriamine, and triethylenetetramine.   The flame retardant containing the compound as described in any one of Claims 1-3.   The flame retardant according to claim 4, which is used for a thermoplastic resin.   The thermoplastic resin is selected from the group consisting of polyester resins, polyolefin resins, vinyl resins, polycarbonate resins, acrylic resins, styrene resins, polyamide resins, polyphenylene oxide resins, and polyphenylene sulfide resins. The flame retardant according to claim 5, which is at least one kind.   The flame-retardant resin composition containing 1-50 mass parts of flame retardants as described in any one of Claims 4-6 with respect to 100 mass parts of thermoplastic resins.   The flame-retardant resin composition according to claim 7 containing glass fiber.

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