TW202028443A - Flame retardant, flame retardant composition, synthetic-resin composition, and molded object - Google Patents

Abstract

The purpose of the present invention is to provide a flame retardant which has excellent heat resistance and which, when added to synthetic resins, in particular, polyester-based resins, is capable of greatly improving the flame retardancy of the synthetic resins. The flame retardant comprises a compound represented by general formula (1). In general formula (1), R1 and R3 each independently represent a monovalent aromatic group optionally having one or more substituents; X1 and X2 each independently represent a direct bond, a C1-8 alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom, any adjoining carbon atoms of the C1-8 alkylene group optionally having an oxygen, nitrogen, or sulfur atom interposed therebetween; R2 represents -CH2CH2- or -CH2CH2CH2-; and n is a number of 1-10,000.

Description

Flame retardant, flame retardant composition, synthetic resin composition and molded body

The present invention relates to a flame retardant containing a pentaerythritol phosphonate polymer having a specific structure and a synthetic resin composition containing the flame retardant.

Previously, synthetic resins were widely used in automobile parts, packaging materials, building materials, agricultural materials, home appliances, toys, etc. due to their excellent chemical and mechanical properties. Among synthetic resins, especially polypropylene resin, polyethylene resin, polyester resin, polycarbonate resin, ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene) resin, styrene resin, polyamide resin and Polyphenylene ether resins are widely used due to their physical properties. However, these synthetic resins are flammable, so in order to be used for the above-mentioned purposes, in addition to chemical properties and mechanical properties, flame resistance is also required.

As a method of making synthetic resin flame retardant, it is widely known to use halogen flame retardant, inorganic phosphorus flame retardant represented by polyphosphoric acid flame retardant such as red phosphorus or ammonium polyphosphate, magnesium hydroxide Or metal hydroxide-based flame retardants such as aluminum hydroxide, organic phosphorus-based flame retardants represented by triaryl phosphate compounds, and antimony oxide and melamine compounds as flame retardant additives are used alone or in combination.

However, halogen-based flame retardants have safety issues such as generating large amounts of corrosive gas during molding or burning. Inorganic phosphorus-based flame retardants are processed because they generate toxic gases during combustion, or have poor water resistance and heat resistance. There are problems with operation or formability. In addition, metal hydroxide-based flame retardants have the following problems. In order to obtain sufficient flame retardancy, they must be added in large amounts, and the original physical properties of synthetic resins are lost. Organic phosphoric acid-based flame retardants are widely known as flame retardants that do not contain halogen. However, due to the reduced heat resistance of the synthetic resin composition or the lower heat resistance of the flame retardant itself, there are problems in handling during processing .

On the other hand, various studies have been conducted on the use of disubstituted pentaerythritol diphosphonate compounds as flame retardants. For example, Patent Documents 1 and 2 describe that pentaerythritol diphosphonate having a specific structure can be produced by an industrially advantageous and highly productive method, and this pentaerythritol diphosphonate imparts flame retardancy to synthetic resins. However, with regard to the pentaerythritol diphosphonate, it is difficult to obtain sufficient flame retardancy, especially in polyester resins that require high flame retardancy. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2003-267984 Patent Document 2: Japanese Patent Laid-Open No. 2004-210968

The subject of the present invention is to provide a novel flame retardant, which has excellent heat resistance equal to or higher than the previously used flame retardant, and can impart good flame retardancy to synthetic resins.

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive research and found that a specific phosphonic acid having a pentaerythritol skeleton exhibits excellent heat resistance and flame resistance. The present invention has been completed based on the above-mentioned knowledge, and specifically it is as follows.

[Invention 1] A flame retardant containing one or more compounds represented by the following general formula (1).

[化1]

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group that may have one or more substituents, and X ¹ and X ² each independently represent a direct bond, with 1 to 8 carbon atoms The alkylene group, oxygen atom, nitrogen atom or sulfur atom exists in the case where there is an oxygen atom, nitrogen atom or sulfur atom between any adjacent carbon atoms in the alkylene group with 1 to 8 carbon atoms, R ² represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -, and n represents a number from 1 to 10,000.

[Invention 2] The flame retardant as described in Invention 1, wherein in the general formula (1), R ¹ and R ³ are each independently a monocyclic aromatic hydrocarbon ring group.

[Invention 3] The flame retardant as described in Invention 1 or 2, wherein in the general formula (1), X ¹ and X ² are each independently an alkylene group having 1 to 4 carbon atoms.

[Invention 4] A flame retardant composition containing the flame retardant as described in Invention 1 and a phosphate compound.

[Invention 5] The flame retardant composition according to Invention 4, wherein the phosphate compound is a pyrophosphate.

[Invention 6] The flame retardant composition according to Invention 4 or 5, wherein the mass ratio of the flame retardant to the phosphate compound is 9:1 to 1:9.

[Invention 7] A synthetic resin composition containing a synthetic resin and 0.01-50 parts by mass relative to 100 parts by mass of the synthetic resin of the flame retardant according to any one of Inventions 1 to 3.

[Invention 8] A synthetic resin composition containing a synthetic resin and the flame retardant composition according to any one of Inventions 4 to 6 in an amount of 0.01-100 parts by mass relative to 100 parts by mass of the synthetic resin.

[Invention 9] The synthetic resin composition according to Invention 7 or 8, wherein the synthetic resin contains at least one selected from the group of polyester resins and polyamide resins.

[Invention 10] A molded product obtained from the synthetic resin composition according to any one of Inventions 7 to 9.

於通式(1)中，R¹ 及R³ 分別獨立地表示可具有1個以上之取代基之1價芳香族基， X¹ 及X² 分別獨立地表示直接鍵、碳原子數1～8之伸烷基、氧原子、氮原子或硫原子，存在於該碳原子數1～8之伸烷基中之任意相鄰之碳原子間介存有氧原子、氮原子或硫原子之情形， R² 表示-CH₂ CH₂ -或-CH₂ CH₂ CH₂ -， n表示1～10000之數。 [發明之效果][Invention 11] A method for flame-retarding synthetic resin by adding a compound represented by the following general formula (1) to the synthetic resin. [化1A]

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group that may have one or more substituents, and X ¹ and X ² each independently represent a direct bond, with 1 to 8 carbon atoms The alkylene group, oxygen atom, nitrogen atom or sulfur atom exists in the case where there is an oxygen atom, nitrogen atom or sulfur atom between any adjacent carbon atoms in the alkylene group with 1 to 8 carbon atoms, R ² represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -, and n represents a number from 1 to 10,000. [Effects of Invention]

The flame retardant of the present invention has excellent heat resistance, and by adding to synthetic resins, especially polyester resins, the flame retardancy of synthetic resins can be greatly improved.

Hereinafter, the present invention will be described in detail based on its preferred embodiments. First, the flame retardant of the present invention will be explained. The flame retardant of the present invention contains one or more compounds represented by the following general formula (1). [化2]

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group that may have one or more substituents, and X ¹ and X ² each independently represent a direct bond, with 1 to 8 carbon atoms The alkylene group, oxygen atom, nitrogen atom or sulfur atom exists in the case where there is an oxygen atom, nitrogen atom or sulfur atom between any adjacent carbon atoms in the alkylene group with 1 to 8 carbon atoms, R ² represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -, and n represents a number from 1 to 10,000.

Examples of the monovalent aromatic group represented by R ¹ and R ³ in the general formula (1) include an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms . The above-mentioned aromatic hydrocarbon ring group having 6 to 20 carbon atoms may be a monocyclic ring or a condensed ring. As a monocyclic aromatic hydrocarbon ring group, a phenyl group, a biphenyl group, a triphenyl group, etc. are mentioned, for example. Examples of the aromatic hydrocarbon ring group of the condensed ring include a naphthyl group, a stilbene group, and a pyrenyl group. Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include furyl, thienyl, benzopiperanyl, benzothienyl, difuranyl, trifuranyl, dithienyl, and trithienyl , Selenophene, diselenyl and triselenophene, etc. Among these aromatic groups, in terms of flame retardancy and compatibility with resins, R ¹ and R ^{3 are} preferably aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, more preferably monocyclic The aromatic hydrocarbon ring group is more preferably phenyl. The number of carbon atoms of the aromatic group is preferably 6-10.

When the monovalent aromatic group has a substituent, examples of the substituent include an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be chain or cyclic. The chain alkyl group may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and 1-octyl. Examples of branched alkyl groups include isopropyl, second butyl, tertiary butyl, isobutyl, isopentyl, tertiary pentyl, 2-hexyl, 3-hexyl, and 2-heptyl. Base, 3-heptyl, isoheptyl, third heptyl, isooctyl and third octyl, etc. Examples of the cyclic alkyl group include cyclohexyl and 1-methylcyclohexyl. In the present invention, the above-mentioned substituent is preferably a linear alkyl group from the viewpoint of flame retardancy and compatibility with resin. The number of carbon atoms of the linear alkyl group is preferably 1 to 4, more preferably 1, that is, a methyl group.

When R ¹ and/or R ³ in the general formula (1) is a phenyl group, and the phenyl group is substituted by one of the above-mentioned alkyl groups, the substitution position of the alkyl group can be ortho, meta and para positions Of either type, counterpoint is particularly preferred. When R ¹ and/or R ³ in the general formula (1) is a phenyl group, and the phenyl group is substituted by two of the above-mentioned alkyl groups, the substitution position of the alkyl group can be ortho, meta and para positions Either of these, the indirect position is particularly preferred.

As the alkoxy group having 1 to 8 carbon atoms, for example, a group having an oxygen atom bonded to the terminal of the above-mentioned alkyl group having 1 to 8 carbon atoms is mentioned. When R ¹ and/or R ³ in the general formula (1) is a phenyl group and the phenyl group is substituted by one of the above-mentioned alkoxy groups, the substitution position of the alkoxy group may be ortho, meta or Any kind of counterpoint, especially counterpoint. When R ¹ and/or R ³ in the general formula (1) is a phenyl group, and the phenyl group is substituted by two of the above-mentioned alkoxy groups, the substitution position of the alkoxy group may be ortho, meta or Any kind of counterpoint is especially preferred.

In the general formula (1), the alkylene group having 1 to 8 carbon atoms represented by X ¹ and X ² may be linear or branched. Specific examples of the alkylene group include, for example, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, 1,3-butanediyl group, 2-methyl-1,3 -Propanediyl, 2-methyl-1,3-butanediyl, 2,4-pentanediyl, 1,4-pentanediyl, 3-methyl-1,4-butanediyl, 2-methyl Group-1,4-pentamethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene, etc. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms, from the viewpoint of flame retardancy and compatibility with the resin. Preferably, it is an alkylene group having a carbon number of 1, that is, a methylene group.

There are cases in which oxygen atoms, nitrogen atoms or sulfur atoms are interposed between any adjacent carbon atoms in the above-mentioned alkylene. In the compound represented by the general formula (1), on condition that the oxygen atom, nitrogen atom or sulfur atom are not adjacent to each other, it is present in one or more positions of the alkylene group with intervening oxygen atoms and nitrogen. In the case of one or more heteroatoms among atoms or sulfur atoms.

In the compound represented by the general formula (1), R ¹ is preferably a phenyl group and X ¹ is a methylene group, that is, a benzyl group is formed by R ¹ and X ¹ . In addition, in the compound represented by the general formula (1), it is preferable that R ³ is a phenyl group and X ² is a methylene group, that is, R ³ and X ² form a benzyl group.

R ² in the general formula (2) represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -. From the viewpoint of heat resistance, R ^{2 is} preferably -CH ₂ CH ₂ -.

In the general formula (1), n represents a number from 1 to 10,000, preferably a number from 3 to 10,000, and more preferably a number from 5 to 10,000. From the viewpoint of heat resistance, flame retardancy, and compatibility, Preferably it is a number from 10 to 10,000. The flame retardant of the present invention may include only a single compound in which n is one, and a mixture of two or more compounds in which n is different. As the flame retardant of the present invention, when n is a mixture of two or more different types, the number of n can be expressed by an average value (based on the number of moles).

The number of n in the compound represented by the general formula (1) contained in the flame retardant of the present invention can be measured, for example, by gel permeation chromatography (GPC) or nuclear magnetic resonance analysis (NMR).

The compound represented by the general formula (1) contained in the flame retardant of the present invention can be produced by a method according to a known method for producing pentaerythritol phosphonate. For example, as a starting material, a compound represented by the following general formula (A) and a compound represented by the general formula (B-1) or (B-2) are used, and the reaction is carried out under heating in a solvent. polymerization. As the solvent, for example, toluene, xylene, monochlorobenzene, dichlorobenzene, propylene carbonate, ethylene carbonate, cyclobutylene, diethylene glycol dimethyl ether, etc. can be used. For stopping the polymerization, the compound represented by the general formula (C) may be added to the reaction system.

[化3]

In the general formula (A), R ^a and R ^b each independently represent the number of carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, second butyl, tertiary butyl, and isobutyl 1 ~4 alkyl.

[化4]

In the general formula (B-1), Y ^a represents ^a halogen atom such as chlorine, bromine, and iodine. [化5]

In the general formula (B-2), Y ^a represents ^a halogen atom such as chlorine, bromine, and iodine. [化6]

In the general formula (C), R ^C represents the same groups as R ¹ and R ³ in the general formula (1), that is, represents a monovalent aromatic group that may have one or more substituents. X ^a represents the same groups as X ¹ and X ² in the general formula (1), that is, represents an alkylene group having 1 to 8 carbon atoms. Y ^b represents a halogen atom such as chlorine, bromine, and iodine.

As the compound of the present invention represented by the general formula (1) used as a flame retardant, for example, the group of compounds represented by the following No. 1 to No. 4 can be cited, but it is not particularly limited to these, as long as the general formula is used (1) Means that these derivatives can also be used. Among them, the compound of No. 1 is preferred in terms of heat resistance and flame retardancy.

[化7]

In No. 1, n represents a number from 1 to 10,000.

[化8]

In No. 2, n represents a number from 1 to 10,000.

[化9]

In No. 3, n represents a number from 1 to 10,000.

[化10]

In No. 4, n represents a number from 1 to 10,000.

The flame retardant of the present invention may contain only one compound represented by the general formula (1), or two or more kinds.

Next, the flame retardant composition of the present invention will be described. The flame retardant composition of the present invention contains the compound represented by the above general formula (1) and a phosphate compound. The flame retardant composition of the present invention can impart excellent flame retardancy to synthetic resins. The flame retardant composition of the present invention may contain only one compound represented by the above general formula (1), or may contain two or more kinds. By using the flame retardant of the present invention in combination with one or more phosphate compounds, it has the effect of imparting excellent flame retardancy to synthetic resins.

As the phosphate compound used in the flame retardant composition of the present invention, for example, phosphates such as melamine phosphate and piperidine phosphate; polyphosphates such as ammonium polyphosphate, melamine polyphosphate and piperidine polyphosphate; orthophosphoric acid Orthophosphates such as melamine and piperidine orthophosphate; pyrophosphates such as ammonium pyrophosphate, melamine pyrophosphate and piperidine pyrophosphate; calcium phosphate; magnesium phosphate and their derivatives. The flame retardant composition of the present invention may contain only one kind of these phosphate compounds, or two or more kinds. From the viewpoint of flame retardancy and processability, the phosphate compound used in the flame retardant composition of the present invention preferably contains pyrophosphate.

In terms of flame retardancy, the mass of the compound represented by the general formula (1) and the phosphate compound in the flame retardant composition of the present invention is preferably 9:1 to 1: 9, more preferably 8:2 to 2:8, even more preferably 7:3 to 3:7, most preferably 5:5.

As described above, the flame retardant composition of the present invention can be preferably used as a flame retardant for imparting flame retardancy to synthetic resins. In addition to the compound represented by the general formula (1) and the phosphate compound, the flame retardant composition of the present invention may also contain other additives.

As the above-mentioned other additives, as long as the effects of the present invention are not impaired, well-known additives used in the technical field of the present invention can be used, and well-known additives can be formulated in any addition amount. As the above-mentioned other additives, for example, used are selected from phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, other antioxidants, hindered amine-based light stabilizers, ultraviolet absorbers, plasticizers, nucleating agents, and deodorizers. One or more of flame retardants, flame retardant additives, lubricants, fillers, hydrotalcites, metal soaps, antistatic agents, pigments and dyes other than the flame retardants of the invention. These other additives can be directly formulated into the flame retardant composition, or when being formulated into the synthetic resin, they can be separately formulated into the synthetic resin from the flame retardant composition.

As said phenolic antioxidant, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, (3,5-di-tert-butyl) 4-hydroxyphenyl) stearyl propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 3,5-di-tert-butyl-4- Tridecyl hydroxybenzyl thioacetate, thiodiethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl m-cresol), 2-octylthio-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-tris, 2,2 '-Methylenebis(4-methyl-6-tertiary butylphenol), bis[3,3-bis(4-hydroxy-3-tertiarybutylphenyl)butyric acid]diol ester, 4 ,4'-butylene bis(4,6-di-tertiary butylphenol), 2,2'-ethylene bis(4,6-di-tertiary butylphenol), 1,1,3-tris( 2-Methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-third Butyl-5-methylbenzyl)phenyl) ester, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, isocyanuric acid 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) cyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Yl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxyethyl]isocyanurate , Tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-propylene Acetooxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl) Propyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane and triethylene glycol bis[β-(3-tertiary butyl) 4-hydroxy-5-methylphenyl)propionate] and so on. These phenolic antioxidants may be used individually by 1 type, and may use 2 or more types together. The content of the phenolic antioxidant in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the synthetic resin is 0.01 to 1 part by mass, more preferably 0.03 to 0.8 part by mass.

Examples of the phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, hepta(dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, Diisooctylphenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, two Isodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tri(isodecyl) phosphite, tri(isodecyl) phosphite Tridecyl) ester, diphenyldecyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyldipropylene glycol diethylene Phosphate, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methyl) Phenyl) ester, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl) phosphite, phosphorous acid Tris(decyl) ester, octyl diphenyl phosphite, bis(decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, distearyl pentaerythritol and calcium stearate Mixture, alkyl (C10) bisphenol A phosphite, di(tridecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tertiary butyl) Phenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) ) Pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2, 4-Di-tert-butyl-6-methylphenyl) ethyl ester, tetrakis (tridecyl) isopropylidene diphenol diphosphite, 4,4'-n-butylene bis(2-third Butyl-5-methylphenol) tetratridecyl diphosphite, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triethylene Hexa(tridecyl) phosphate, tetrakis(2,4-di-tert-butylphenyl) biphenyl diphosphonite, 9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene) tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexa (Tridecyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylene Bis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylene bis(4,6-di-tert-butylphenyl) fluorophosphite, 4,4'-butylene bis(3-methyl-6-tert-butylphenyl bis(tridecyl)) phosphite, tris(2-[(2,4,8,10-fourth Tributyl dibenzo[d,f][1,3,2]dioxaphosphorine-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6- Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidene diphenol C12-15 alcohol phosphite, etc. These phosphorus antioxidants may be used individually by 1 type, and may use 2 or more types together. The content of the phosphorus-based antioxidant in the flame retardant composition of the present invention can be set in a range that does not impair the effect of the present invention, and is preferably relative to that contained in the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass of the synthetic resin is 0.01 to 1 part by mass, more preferably 0.03 to 0.8 part by mass.

Examples of the above-mentioned thioether antioxidant include tetra[methylene-3-(laurylthio)propionate]methane and bis(methyl-4-[3-n-alkyl(C12/C14) Thiopropionyloxy)5-tert-butylphenyl)sulfide, 3,3'-thiodipropionate di(tridecyl)ester, 3,3'-thiodipropionate dilaurin Esters, 3,3'-dimyristyl thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl/stearyl thiodipropionate, 4,4'-thio Bis (6-tertiary butyl m-cresol), 2,2'-thiobis (6-tertiary butyl p-cresol), distearyl disulfide. These thioether antioxidants may be used individually by 1 type, and may use 2 or more types together. The content of the thioether antioxidant in the flame retardant composition of the present invention can be set within a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass of the synthetic resin is 0.001-10 parts by mass, more preferably 0.005-5 parts by mass.

As the above hindered amine light stabilizer, for example, stearic acid 2,2,6,6-tetramethyl-4-piperidinate, stearic acid 1,2,2,6,6-pentamethyl -4-piperidinyl ester, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate Esters, 1,2,3,4-butanetetracarboxylic acid tetra(2,2,6,6-tetramethyl-4-piperidyl) ester, 1,2,3,4-butanetetracarboxylic acid Tetra(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,2,3,4-butanetetracarboxylic acid bis(2,2,6,6-tetramethyl) -4-piperidinyl)-bis(tridecyl)ester, 1,2,3,4-butanetetracarboxylic acid bis(1,2,2,6,6-pentamethyl-4-piperidine Yl)-bis(tridecyl) ester, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5- Di-tert-butyl-4-hydroxybenzyl) ester, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate condensation polymer, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2,4-dichloro-6-𠰌line-s-tri-condensate, 1, 6-Bis(2,2,6,6-Tetramethyl-4-piperidinylamino)hexane/2,4-dichloro-6-third octylamino-s-triscondensate, 1,5,8,12-Tetra[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-tri𠯤 -6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(1,2,2 ,6,6-Pentamethyl-4-piperidinyl)amino)-s-tris-6-yl)-1,5,8-12-tetraazadodecane, 1,6,11- Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-tris-6-yl]amino Monoalkane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s -Tris(6-yl)aminoundecane, sebacic acid bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}ester, bis{4 -(2,2,6,6-Tetramethyl-1-undecyloxy)piperidinyl} ester, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals, etc. These hindered amine light stabilizers may be used individually by 1 type, and may use 2 or more types together. The content of the hindered amine-based light stabilizer can be set in a range that does not impair the effect of the present invention, and is preferably relative to 100 parts by mass of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass.

As the above-mentioned ultraviolet absorber, for example, 2-hydroxydibenzophenone such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone) Benzophenones; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-third octylphenyl)benzotriazole, 2-(2- Hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzo Triazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tertiary octyl-6-benzotriazole Phenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-propenyloxy) Ethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloxyethyl)-5-tert-butylphenyl]benzo Triazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-third octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2 -Methacryloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloxyethyl) Phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy -3-Third-pentyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methyl Allyloxypropyl) phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloxymethyl)phenyl]benzotriazole, 2 -[2-Hydroxy-4-(3-methacryloxy-2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloxy Propyl) phenyl] benzotriazole and other 2-(2-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 3,5-di-tertidine 2,4-di-tert-butyl phenyl 4-hydroxybenzoate, (3,5-di-tert-butyl-4-hydroxy) octyl benzoate, (3,5-di-tert-butyl- 4-hydroxy)dodecyl benzoate, (3,5-di-tert-butyl-4-hydroxy) tetradecyl benzoate, (3,5-di-tert-butyl-4-hydroxy) Cetyl benzoate, (3,5-di-tert-butyl-4-hydroxy) octadecyl benzoate, (3,5-di-tert-butyl-4-hydroxy) behenate Esters and other benzoic acid esters; 2-ethyl-2'-ethoxy oxaniline, 2-ethoxy-4'-dodecyl oxaniline and other substituted oxaniline; α- Cyanoacrylates such as cyano-β,β-diphenyl ethyl acrylate, 2-cyano-3-methyl-3-(p-methoxyphenyl) methyl acrylate, etc.; various metal salts or metal chelate Compounds, especially salts or chelate compounds of nickel and chromium. These ultraviolet absorbers may be used individually by 1 type, and may use 2 or more types together. The content of the ultraviolet absorber in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin composition contained in the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the resin is 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass.

As said plasticizer, for example, dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, ortho Phthalic acid esters such as diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, etc. Agents; Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(diethylene glycol butyl ether) adipate; three phosphate Phenyl ester, tricresyl phosphate, tris(xylene) phosphate, tris(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris(butoxyethyl) phosphate Phosphate plasticizers such as octyl diphenyl phosphate; use ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1, Polyols such as 5-pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid and other dibasic acids, and if necessary, monohydric alcohols, monocarboxylic acids (acetic acid, aromatic acids) Etc.) as terminating agents, polyester plasticizers other than the present invention; epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized Safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, isocyanuric acid Tris(glycidyl) ester, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, diepoxidized cyclohexene ethylene, diepoxidized dicyclohexene , 3,4-epoxycyclohexylmethylepoxycyclohexane carboxylate and other epoxy plasticizers; and tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid Sebacic acid plasticizers such as bis(2-ethylhexyl) ester (DOS) and dibutyl sebacate (DBS), stearic acid plasticizers, citric acid plasticizers, pyromellitic acid Plasticizers, biphenylene polycarboxylic acid plasticizers, aromatic acid ester plasticizers of polyols (trimethylolpropane tribenzoate, etc.), etc. Preferable examples include: polyester plasticizers, phthalate plasticizers, trimellitate plasticizers, adipate plasticizers, and sebacic acid other than the present invention Department of plasticizer, epoxy plasticizer. These plasticizers may be used individually by 1 type, and may use 2 or more types together. The content of the plasticizer in the flame retardant composition of the present invention can be set in a range that does not impair the effect of the present invention, and is preferably relative to the synthetic resin composition contained in the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the resin is an amount of 1 to 90 parts by mass, more preferably an amount of 10 to 80 parts by mass.

Examples of the nucleating agent include sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and carboxylic acids such as disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate. Metal salt, sodium bis(4-tert-butylphenyl) phosphate, sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate and 2,2'-methylene Phosphate metal salts such as lithium bis(4,6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis(methylbenzylidene) sorbitol, bis(p-ethylbenzylidene) sorbitol Alcohol and bis(dimethylbenzylidene) sorbitol and other polyhydric alcohol derivatives, N,N',N''-tris[2-methylcyclohexyl]-1,2,3-propane trimethamide (RIKACLEAR PC1), N,N',N''-tricyclohexyl-1,3,5-benzenetrimethamide, N,N'-dicyclohexyl-naphthalenedimethylamide, 1,3,5-tris( Dimethyl isopropylamino) benzene and other amide compounds. These nucleating agents may be used individually by 1 type, and may use 2 or more types together. The content of the nucleating agent in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin composition contained in the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the resin is an amount of 1 to 90 parts by mass, more preferably an amount of 10 to 80 parts by mass.

Examples of the above-mentioned other flame retardants include: triphenyl phosphate, tricresyl phosphate, tris(xylene) phosphate, tolyl diphenyl phosphate, and tolyl-2,6-bis(xylene) phosphoric acid Esters, resorcinol bis(diphenyl phosphate), (1-methylethylene)-4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetra(2, 6-Dimethylphenyl) phosphate, the aromatic phosphate of the trade names "Adekastab FP-500", "Adekastab FP-600" and "Adekastab FP-800" manufactured by ADEKA Co., Ltd., phenylphosphonic acid two Phosphonates such as vinyl ester, diallyl phenyl phosphonate, (1-butenyl) phenyl phosphonate, phenyl diphenyl phosphinate, methyl diphenyl phosphinate, 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives and other phosphinates, bis(2-allylphenoxy)phosphazene, xylylphosphazene and other phosphazene compounds , Phosphorus flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A epoxy resin, brominated phenol novolac epoxy resin, hexabromobenzene, pentabromo Toluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, Tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy) -1,3,5-Tribromide, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, five acrylate Brominated flame retardants such as bromobenzyl ester and brominated styrene. These flame retardants may be used individually by 1 type, and may use 2 or more types together. The content of the flame retardant in the flame retardant composition of the present invention can be set to a range that does not impair the effect of the present invention, and is preferably relative to the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass of the synthetic resin becomes 1 to 90 parts by mass, more preferably 3 to 80 parts by mass.

As the above-mentioned flame retardant additives, inorganic flame retardant additives and organic flame retardant additives can be cited. Examples of inorganic flame retardant additives include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, and surface treatment products thereof, such as TIPAQUE R-680 (titanium oxide : Ishihara Sangyo Co., Ltd.), Kyowamag 150 (magnesium oxide: Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.), Alcamizer 4 (zinc-modified hydrotalcite: Kyowa Chemical Industry (Stock) Manufacturing) etc. As an organic flame-retardant auxiliary agent, pentaerythritol, dipentaerythritol, etc. are mentioned, for example. These flame retardant additives may be used individually by 1 type, and may use 2 or more types together. The content of the flame-retardant auxiliary in the flame-retardant composition of the present invention can be set in a range that does not impair the effect of the present invention, and is preferably relative to that contained in the synthetic resin composition containing the flame-retardant composition of the present invention 100 parts by mass of the synthetic resin is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

Examples of the lubricant include: unsaturated fatty acid amides such as oleic acid amides and erucic acid amides; saturated fatty acid amides such as behenate amides and stearic acid amides, butyl stearate, and stearin Alcohol, stearic acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, amide stearate, amide oleate, ethylene glycol Base distearate amide and so on. These lubricants may be used individually by 1 type, and may use 2 or more types together. The content of the lubricant in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass is 0.01 to 10 parts by mass, and more preferably 0.03 to 1 parts by mass.

Examples of the above-mentioned fillers include: talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, and clay , Dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite, fibrous basic magnesium sulfate, etc., the particle size can be selected appropriately (in the case of fibrous form, the fiber diameter or fiber length Aspect ratio). In addition, the filler may be surface-treated as needed. These fillers may be used individually by 1 type, and may use 2 or more types together. The content of the filler in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass is 0.01 to 90 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 5 to 40 parts by mass. Among the above fillers, it is particularly preferable to contain glass fibers. When the flame retardant composition of the present invention contains glass fiber, from the viewpoint of processability, the content of glass fiber is preferably relative to that contained in the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass of synthetic resin becomes 10-40 parts by mass.

As the above-mentioned hydrotalcites, for example, a compound salt compound containing magnesium, aluminum, a hydroxyl group, a carbonate group, and any water of crystallization, which is known as a natural product or a synthetic product, is exemplified: part of magnesium or aluminum is substituted with an alkali metal Or those with other metals such as zinc, or those having hydroxyl groups and carbonate groups substituted with other anionic groups. Specifically, for example, the metal of the hydrotalcite represented by the following general formula (2) is substituted with an alkali metal. In addition, it may be obtained by dehydrating crystal water, or it may be a higher fatty acid metal salt such as a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, Coated with higher fatty acid amide, higher fatty acid ester or wax. These may be natural products or synthetic products, and they may be used without being limited to crystal structures and crystal particles. These hydrotalcites may be used individually by 1 type, and may use 2 or more types together. The content of the hydrotalcite in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin composition contained in the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the resin is 0.01 to 90 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 5 to 40 parts by mass.

Examples of the metal soap include salts of metals such as magnesium, calcium, aluminum, and zinc and saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. These metal soaps may be used individually by 1 type, and may use 2 or more types together. The content of the metal soap in the flame retardant composition of the present invention can be formulated within a range that does not impair the effects of the present invention, and is preferably relative to the amount contained in the synthetic resin composition containing the flame retardant composition of the present invention 100 parts by mass of the synthetic resin is 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salt and polyamine quaternary salt; higher alcohol phosphate ester salt, higher alcohol EO (Ethylene Oxide) adduct, poly Ethylene glycol fatty acid ester, anionic alkyl sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide adduct sulfate ester salt, higher alcohol ethylene oxide adduct phosphate ester salt, etc. Electrostatic agent; non-ionic antistatic agent such as polyol fatty acid ester, polyglycol phosphate ester, polyoxyethylene alkyl allyl ether; amphoteric type alkyl betaines such as alkyl dimethyl amino acetic acid betaine, imidazole Amphoteric antistatic agents such as morpho-type amphoteric active agents. These antistatic agents may be used individually by 1 type, and may use 2 or more types together. The content of the antistatic agent in the flame retardant composition of the present invention can be set in a range that does not impair the effect of the present invention, and is preferably relative to the synthetic resin composition contained in the synthetic resin composition containing the flame retardant composition of the present invention. 100 parts by mass of the resin is 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass.

As the above-mentioned pigments, for example, pigments commercially available as pigments can also be used, such as: Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90 , 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220 , 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110 , 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7 , 10, 36; Pigment Blue 15, 15:1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1 , 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These pigments may be used individually by 1 type, and may use 2 or more types together. The content of the pigment in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. The part by mass becomes an amount of 0.001 to 5 parts by mass, more preferably an amount of 0.003 to 3 parts by mass.

染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁𠯤染料、酞菁染料、花青染料等染料等。該等染料可單獨使用1種，亦可併用2種以上。本發明之難燃劑組合物中之顏料之含量可設為不損害本發明之效果之範圍，較佳為相對於含有本發明之難燃劑組合物之合成樹脂組合物所含有之合成樹脂100質量份成為0.001～5質量份之量，更佳為成為0.003～3質量份之量。As the above-mentioned dyes, for example, azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, 𠮿

Dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, 㗁𠯤 dyes, phthalocyanine dyes, cyanine dyes, etc. These dyes may be used individually by 1 type, and may use 2 or more types together. The content of the pigment in the flame retardant composition of the present invention can be set in a range that does not impair the effects of the present invention, and is preferably relative to the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. The part by mass becomes an amount of 0.001 to 5 parts by mass, more preferably an amount of 0.003 to 3 parts by mass.

Next, the synthetic resin composition of the present invention will be explained. The synthetic resin composition of the present invention contains the synthetic resin and the flame retardant of the present invention. The content of the flame retardant of the present invention in the synthetic resin composition of the present invention is 0.01-50 parts by mass relative to 100 parts by mass of the synthetic resin. From the standpoint of flame retardancy, it is preferably 0.05-45 parts by mass, and more It is preferably 1-30 parts by mass. If the content of the flame retardant of the present invention is less than 0.01 parts by mass, the flame retardant effect may become insufficient, and if it is more than 50 parts by mass, the physical properties of the synthetic resin may be impaired.

Furthermore, the synthetic resin composition of the present invention contains a synthetic resin and the flame retardant composition of the present invention. The content of the flame retardant composition of the present invention in the synthetic resin composition of the present invention is 0.01-100 parts by mass relative to 100 parts by mass of the synthetic resin. From the viewpoint of flame retardancy, it is preferably 0.05-95 parts by mass , More preferably in the range of 1 to 90 parts by mass. If the blending amount of the flame retardant composition of the present invention is less than 0.01 parts by mass, the flame retardant effect may become insufficient, and if it is more than 100 parts by mass, the physical properties of the synthetic resin may be impaired.

As the synthetic resin used in the synthetic resin composition of the present invention, for example, thermoplastic resins and thermosetting resins can be cited, and thermoplastic resins can be preferably used. Examples of thermoplastic resins include polyvinyl chloride resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl acetate resins, polyurethane resins, cellulose resins, acrylic resins, AS (Acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, fluorine resin, thermoplastic elastomer, polyamide resin, polyacetal resin, polycarbonate resin, modified poly Phenyl ether resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, polylactic acid resin), cyclic polyolefin resin, polyphenylene sulfide resin, etc. These synthetic resins may be used alone or in combination of two or more kinds. Among these synthetic resins, polyester resins or polyamide resins are preferred, polyester resins are more preferred, and polybutylene terephthalate resin (PBT resin) is particularly preferred.

Examples of the above-mentioned polyester resins include the use of dibasic acids such as terephthalic acid or these derivatives having ester-forming ability as the acid component, the use of diols with 2 to 10 carbon atoms, other diols, or Saturated polyester resins obtained as diol components such as ester-forming derivatives. Among them, polyalkylene terephthalate resin is preferred. Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin.

Examples of the polyamide-based resin include: polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 and other aliphatic polyamides. Amide; alicyclic polyamide obtained from alicyclic diamines such as bis(aminocyclohexyl) C _1-3 alkanes and aliphatic dicarboxylic acids such as C _8-14 alkane dicarboxylic acid; from aromatic Polyamides obtained from tricarboxylic dicarboxylic acids (such as terephthalic acid and/or isophthalic acid) and aliphatic diamines (such as hexamethylene diamine, nonane diamine, etc.); from aromatic and aliphatic dicarboxylic acids (Such as terephthalic acid and adipic acid) and aliphatic diamine (such as hexamethylene diamine) obtained by polyamides and the like.

In the synthetic resin composition of the present invention, as long as the effect of the present invention is not impaired, the above-mentioned other additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, hindered Amine-based light stabilizers, ultraviolet absorbers, plasticizers, nucleating agents, flame retardants, flame retardant additives, lubricants, fillers, hydrotalcites, metal soaps, antistatic agents, pigments, dyes, etc.) or Other well-known resin additives. The content of other additives in the resin composition of the present invention is as described above. The synthetic resin composition of the present invention is characterized by containing the flame retardant of the present invention or the flame retardant composition of the present invention. The method of blending the flame retardant of the present invention or the flame retardant composition of the present invention into the synthetic resin is not particularly limited, and known methods can be used. As a specific compounding method, a method of mixing by a normal mixer, a mixer, etc.; a method of melting and kneading by an extruder, etc.; a method of mixing with a solvent and casting a solution.

Next, the molded product of the present invention will be described. The molded article of the present invention is obtained by molding the synthetic resin composition of the present invention. The method and molding conditions for molding the synthetic resin composition are not particularly limited, and known methods and molding conditions can be adopted. As a specific molding method, extrusion molding, injection molding, stretched film molding, blow molding, etc. can be cited, and these molding methods can be implemented under known molding conditions.

The shape of the molded body obtained by molding the synthetic resin composition of the present invention is not particularly limited, and examples thereof include sheet, film, and special shapes. The use of the obtained molded body is not particularly limited. Examples include: food containers, electronic parts, automobile parts, medical award materials, film/sheet materials, fiber materials, optical materials, resins for coatings, resins for inks, and color enhancers Resin, adhesive resin, etc. [Example]

Hereinafter, the present invention will be explained in more detail using examples. However, the present invention is not limited at all by the following examples.

[Example 1] (Synthesis of Flame Retardant Compound No. 1) 3,9-Dibutoxy-2,4,8,10-Tetraoxa-3,9-Diphosphaspiro [ 5,5] Undecane 54.4 g (0.16 mol), 1,2-dibromoethane 24.42 g (0.13 mol), and cyclobutane 150 ml, react at 150°C for 10 hours. 66.71 g (0.39 mol) of benzyl bromide was further added to the flask and reacted at 150°C for 2 hours. After the reaction, the reaction liquid was cooled to room temperature. The reaction solution cooled to room temperature was transferred to a beaker, and 300 ml of acetone was added to filter. This washing operation was repeated three times. The residue was dried in a vacuum oven at 150°C for 5 hours. A white powder is obtained. The yield is 32.9 g (80.5%). The identification of the obtained compound was performed using ¹ H-NMR and ³¹ P-NMR (measuring device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). The ¹ H-NMR and ³¹ P-NMR of the obtained compound No. ¹ are as follows. The obtained compound No. ¹ calculated an average degree of polymerization n of 47 based on ¹ H-NMR.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 7.40-7.26 (m, 10H, -ph), 4.71-4.02 (m, br, 188H, -CH ₂ O-), 3.51 (d , 4H, ph-CH ₂ -), 2.30-2.01 (m, br, 384H, -CH ₂ -)

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 26.19 (s, -P (= O) -CH ₂ -CH ₂ -), 22.99 (s, -P (= O) -CH ₂ -ph)

[Example 2] (Synthesis of Flame Retardant Compound No. 2) 3,9-Dibutoxy-2,4,8,10-Tetraoxa-3,9-Diphosphaspiro [ 5,5] Undecane 54.4 g (0.16 mol), 1,3-dibromopropane 26.25 g (0.13 mol), and cyclobutane 150 ml, reacted at 150°C for 10 hours. 66.71 g (0.39 mol) of benzyl bromide was further added to the flask and reacted at 150°C for 2 hours. After the reaction, the reaction liquid was cooled to room temperature. The reaction solution cooled to room temperature was transferred to a beaker, and 300 ml of acetone was added to filter. This washing operation was repeated three times. The residue was dried in a vacuum oven at 150°C for 5 hours. A white powder is obtained. The yield is 34.4 g (75.6%). The identification of the obtained compound was performed using ¹ H-NMR and ³¹ P-NMR (measuring device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). The ¹ H-NMR and ³¹ P-NMR of the obtained compound No. 2 are as follows. The obtained compound No. 2 calculated an average degree of polymerization n of 50 based on ¹ H-NMR.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 7.40-7.06 (m, 10H, -ph), 4.39-4.02 (m, br, 300H, -CH ₂ O-), 3.55-3.30 (d, 4H, ph-CH ₂ -), 2.30-2.01 (m, br, 408H, -CH ₂ -)

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 26.19 (s, -P (= O)-CH ₂ -CH ₂ -), 22.99 (s, -P (= O) -CH ₂ -ph)

[Comparative Example 1] (Synthesis of Comparative Compound A) The comparative compound A shown below was synthesized by the method described below. [化11]

Add 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 54.3 g (0.16 mol), 1, 28.10 g (0.13 mol) of 4-dibromobutane and 150 ml of ethylene carbonate were reacted at 150°C for 7 hours. Then, 66.71 g (0.39 mol) of benzyl bromide was added to the flask, and the reaction was carried out at 150°C for 2 hours. Purification was performed by the same procedure as that performed in the synthesis of compound No.1. The yield was 33.71 g (71.2%). The compound thus obtained is referred to as comparative compound A. The identification of the obtained compound was performed by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound A are as follows. Comparative compound A calculated an average degree of polymerization n of 43 from ¹ H-NMR.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 7.27-7.18 (m, 10H, ph-), 4.34-4.05 (m, 352H, -CH ₂ O-) 3.44, 3.39 (d, 10H, ph-CH ₂ -), 1.35-1.27, 0.82-0.79 (m, 348H, -CH ₂ -)

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 29.66-28.97, 23.20 -22.78

[Comparative Example 2] (Synthesis of Comparative Compound B) The comparative compound B shown below was synthesized by the method described below.

[化12]

Add 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 54.3 g (0.16 mol), 1, 28.10 g (0.13 mol) of 4-dibromobutane and 150 ml of propylene carbonate were reacted at 150°C for 7 hours. 53.50 g (0.39 mol) of bromobutane was further added to the flask, and reacted under reflux of bromobutane for 8 hours. Purification was performed by the same procedure as that performed in the synthesis of compound No.1. The yield is 27.12 g (65.5%). The compound thus obtained is referred to as comparative compound B. The identification of Comparative Compound B was performed by ¹ H-NMR and ³¹ P-NMR (measuring device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound B are as follows. Comparative compound B calculated an average degree of polymerization n of 45 based on ¹ H-NMR.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 4.39-4.19 (m, 368H, -CH ₂ O-), 2.09-1.87, 1.51-1.36 (m, 372H, -CH ₂ -) , 0.91-0.87 (m, 6H, -CH ₃ )

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 28.97-24.49

[Comparative Example 3] (Synthesis of Comparative Compound C) The comparative compound C shown below was synthesized by the method described below.

[化13]

Add 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 54.4 g (0.16 mol), α, 34.3 g (0.13 mol) of α'-dibromopara-xylene and 150 ml of diethyl oxalate were reacted at 150°C for 5 hours. After the reaction, the reaction liquid was cooled to room temperature. 54.71 g (0.40 mol) of bromobutane was further added to the flask, and the temperature was increased until bromobutane was refluxed and reacted for 8 hours. Thereafter, purification was performed in the same procedure as that performed in the synthesis of compound No.1. The yield was 39.24 (68.2%). The compound thus obtained is referred to as comparative compound C. The identification of the obtained compound was performed by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound C are as follows. Comparative compound C calculated the average degree of polymerization n from ¹ H-NMR to be 48.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 7.26-7.20 (m, 192H, -ph-), 4.59-3.45 (m, 392H, -CH ₂ O-) 3.50-3.45 (d , br, 192H, ph-CH ₂ -), 0.91-0.87 (m, 12H, -CH ₂ -), 0.92-0.84 (m, 6H, -CH ₃ )

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 29.84-29.32, 23.30 22.65

[Comparative Example 4] (Synthesis of Comparative Compound D) The comparative compound D shown below was synthesized by the method described below.

[化14]

Add 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane 57.34 g (0.16 mol), benzyl to the flask Bromine 125.6 g (0.80 mol), react at 150°C for 3 hours. After the reaction, the benzyl bromide was distilled off under reduced pressure. The obtained powder was dispersed in 50 g of acetone, stirred for 30 minutes, and the dispersion was filtered. This washing operation was repeated three times. It was dried at 150°C for 5 hours under reduced pressure. The yield was 55.87 g (80.1%). The obtained compound is referred to as comparative compound D. The identification of the comparative compound D was performed by ¹ H-NMR and ³¹ P-NMR (measuring device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Co., Ltd.). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound D are as follows.

¹ H-NMR (CDCl ₃ , 400 MHz): δ (ppm) 7.35-7.22 (m, 10H, -ph-), 4.15-4.11, 4.05-4.01, 3.74-3.66, 3.51-3.43 (Dd, Dd, Dd , Dd, 8H, -CH ₂ O-), 3.28, 3.23 (d, 4H, -CH ₂ -)

³¹ P-NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 28.97-24.49

The heat resistance of the compounds synthesized in Examples 1 and 2 and Comparative Examples 1 to 4 was evaluated by the following heat resistance evaluation method. The results are shown in Table 1.

[Method of evaluating heat resistance] Using thermogravimetric-differential thermal analysis device Thermo plus EVO (manufactured by Rigaku Co., Ltd.), the above-mentioned compounds No. 1 and 2 and comparative compounds A to D were subjected to a nitrogen gas flow of 200 ml/min at a heating rate of 10°C/min. Raise the temperature from 30°C to 450°C, and measure the 1% weight and 5% weight loss temperature.

[Table 1] Heat resistance 1% weight reduction temperature (℃) 5% weight reduction temperature (℃) Example 1 Compound No.1 307 355 Example 2 Compound No. 2 238 309 Comparative example 1 Comparative compound A 243 335 Comparative example 2 Comparative compound B 229 282 Comparative example 3 Comparative compound C 220 319 Comparative example 4 Comparative compound D 259 321

It can be seen from Table 1 that the compound No. 1 contained in the flame retardant of the present invention synthesized in Example 1 has good heat resistance compared with the comparative compounds A to D synthesized in Comparative Examples 1-4. In addition, the compound No. 2 included in the flame retardant of the present invention synthesized in Example 2 has excellent heat resistance that is approximately the same as that of the comparative compounds A to D synthesized in Comparative Examples 1-4.

[Examples 3-10 and Comparative Examples 5-8] The components described in Table 2 below were blended with the blending amounts (% by mass) described in Table 2 to obtain a synthetic resin composition. Using this synthetic resin composition, the flame retardancy was evaluated by the following evaluation method. The results are shown in Table 2.

[Inflammability (UL-94V) Evaluation Method] The synthetic resin composition was pressurized for 15 minutes under the conditions of 280° C. and 5-15 MPa to obtain a test piece for the flame retardancy test evaluation with a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm. For the obtained test piece, according to ISO1210 and according to the 20 mm vertical burning test (UL-94V), the test piece is kept vertical, the flame of the burner is ignited for 10 seconds and then the flame is removed, and the time for the burning fire of the test piece to extinguish. Next, while the fire is extinguished, the second ignition is performed for 10 seconds, and the time to extinguish the burning fire is measured in the same manner as the first time. At the same time, it was also evaluated whether the cotton under the test piece caught fire due to the falling fire. According to the first and second burning time, whether the cotton is on fire, etc., the burning level is evaluated according to the UL-94V standard. Regarding the combustion level, V-0 is the highest, and the flame retardancy of V-1 and V-2 is lower in order.

[Table 2] Example 3 4 5 6 7 8 9 10 PBT resin ^{﹡ 1} 50 50 50 50 50 51.25 52.5 50 Glass fiber ^{﹡ 2} 30 30 30 30 30 30.75 31.5 30 Compound No.1 14 12 10 8 6 9 8 Compound No. 2 10 Melamine pyrophosphate ^{* 3} 6 8 10 12 14 9 8 10 Comparative compound A Comparative compound B Comparative compound C Comparative compound D Flammability (UL-94V) V-1 V-0 V-0 V-0 V-1 V-0 V-1 V-0 Comparative example 5 6 7 8 PBT resin ^{﹡ 1} 50 50 50 50 Glass fiber ^{﹡ 2} 30 30 30 30 Compound No.1 Compound No. 2 Melamine pyrophosphate ^{* 3} 10 10 10 10 Comparative compound A 10 Comparative compound B 10 Comparative compound C 10 Comparative compound D 10 Flammability (UL-94V) V-1 V-2 V-1 V-2 ﹡1: Duranex (manufactured by Polyplastics (stock)) ﹡2: Chopped Strand (fiber length 3 mm, filament diameter 11 μm) ﹡3: the ratio of pyrophosphate to melamine is 1:2 (molar ratio)

It can be seen from Table 2 that the synthetic resin compositions of Examples 5 and 10 using the flame retardant (flame retardant resin composition) of the present invention have good flame retardancy compared with the synthetic resin compositions of Comparative Examples 5 to 8 The synthetic resin compositions of Comparative Examples 5 to 8 used Comparative Compounds A to D as flame retardants, except that they had the same composition as Examples 5 and 10. From this, it was clarified that by the flame retardant (flame retardant resin composition) of the present invention, a synthetic resin having good flame retardancy can be obtained.

Claims (11)

A flame retardant, which contains a compound represented by the following general formula (1), [化1]

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group that may have one or more substituents, and X ¹ and X ² each independently represent a direct bond, with 1 to 8 carbon atoms The alkylene group, oxygen atom, nitrogen atom or sulfur atom exists in the case where there is an oxygen atom, nitrogen atom or sulfur atom between any adjacent carbon atoms in the alkylene group with 1 to 8 carbon atoms, R ² represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -, and n represents a number from 1 to 10,000. The flame retardant of claim 1, wherein in the general formula (1), R ¹ and R ³ are each independently a monocyclic aromatic hydrocarbon ring group. The flame retardant of claim 1, wherein in the general formula (1), X ¹ and X ² are each independently an alkylene group having 1 to 4 carbon atoms. A flame retardant composition containing the flame retardant and a phosphate compound as claimed in claim 1. The flame retardant composition of claim 4, wherein the phosphate compound is a pyrophosphate. The flame retardant composition of claim 4, wherein the mass ratio of the flame retardant to the phosphate compound is 9:1 to 1:9. A synthetic resin composition containing a synthetic resin and 0.01-50 parts by mass relative to 100 parts by mass of the synthetic resin of the flame retardant according to claim 1. A synthetic resin composition containing a synthetic resin and 0.01-100 parts by mass relative to 100 parts by mass of the synthetic resin, the flame retardant composition according to claim 4. The synthetic resin composition according to claim 7 or 8, wherein the synthetic resin is at least one selected from the group consisting of polyester resins and polyamide resins. A molded product which is a molded product of the synthetic resin composition of claim 7 or 8. A method for flame-retardant synthetic resin, which is to add a compound represented by the following general formula (1) to the synthetic resin, [化2]

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group that may have one or more substituents, and X ¹ and X ² each independently represent a direct bond, with 1 to 8 carbon atoms The alkylene group, oxygen atom, nitrogen atom or sulfur atom exists in the case where there is an oxygen atom, nitrogen atom or sulfur atom between any adjacent carbon atoms in the alkylene group with 1 to 8 carbon atoms, R ² represents -CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ -, and n represents a number from 1 to 10,000.