WO2020075519A1 - 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 C_1-8 alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom, any adjoining carbon atoms of the C_1-8 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 article

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.

Conventionally, synthetic resins have been widely used for automobile parts, packaging materials, building materials, agricultural materials, home appliances, toys, etc. due to their excellent chemical and mechanical properties. In particular, among synthetic resins, polypropylene resin, polyethylene resin, polyester resin, polycarbonate resin, ABS resin, styrene resin, polyamide resin, polyphenylene oxide resin and the like are widely used due to their physical properties. However, since these synthetic resins are flammable, flame retardancy to flame is required in addition to chemical and mechanical properties for use in the above applications.

As a flame retardant method for synthetic resins, halogen-based flame retardants, inorganic phosphorous flame retardants represented by polyphosphoric acid flame retardants such as red phosphorus and ammonium polyphosphate, and metal hydroxides such as magnesium hydroxide and aluminum hydroxide. It is widely known that physical flame retardants, organic phosphorus flame retardants represented by triaryl phosphate ester compounds, and antimony oxide and melamine compounds used alone or in combination as flame retardant aids.

However, halogen-based flame retardants have safety problems such as generating a large amount of corrosive gas during molding and combustion, and inorganic phosphorus-based flame retardants have toxic gas during combustion, water resistance and heat resistance. Since this is inferior, there is a problem in handling during processing and moldability. Further, the metal hydroxide flame retardant needs to be added in a large amount in order to obtain sufficient flame retardancy, and there is a problem that the original physical properties of the synthetic resin are lost. Organic phosphoric acid flame retardants are also widely known as halogen-free flame retardants, but the heat resistance of the synthetic resin composition is reduced, and the heat resistance of the flame retardant itself is low, which causes problems in handling during processing. there were.

On the other hand, various studies have been conducted on the use of disubstituted pentaerythritol diphosphonate compounds as flame retardants. For example, in Patent Documents 1 and 2, a pentaerythritol diphosphonate having a specific structure can be produced by an industrially advantageous method with excellent productivity, and the pentaerythritol diphosphonate makes a synthetic resin flame-retardant. It is described to give. However, with this pentaerythritol diphosphonate, it was difficult to obtain sufficient flame retardancy in a polyester resin that requires particularly high flame retardancy.

JP, 2003-267984, A Japanese Patent Laid-Open No. 2004-210968

An object of the present invention is to provide a novel flame retardant having excellent heat resistance equal to or higher than that of a conventionally used flame retardant, and capable of imparting good flame retardancy to a synthetic resin. .

As a result of intensive studies by the present inventors in order to solve the above problems, it was found that a specific phosphonic acid having a pentaerythritol skeleton exhibits excellent heat resistance and flame retardancy. The present invention has been made based on the above findings, and is specifically as follows.

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

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group which may have one or more substituents,
X ¹ and X ² each independently represent a direct bond, an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a nitrogen atom or a sulfur atom, and are optionally adjacent to each other in the alkylene group having 1 to 8 carbon atoms. Oxygen atom, nitrogen atom or sulfur atom may be present between carbon atoms,
R ² represents —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —,
n represents a number of 1 to 10000.

[Invention 2]
In the general formula (1), R ¹ and R ³ are each independently a monocyclic aromatic hydrocarbon ring group, The flame retardant according to the invention 1.

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

[Invention 4]
A flame retardant composition comprising the flame retardant according to invention 1 and a phosphate compound.

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

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

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

[Invention 8]
A synthetic resin composition containing 0.01 to 100 parts by mass of the flame retardant composition according to any one of Inventions 4 to 6 with respect to 100 parts by mass of the synthetic resin.

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

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

[Invention 11]
A method for flame-retarding a synthetic resin, comprising adding a compound represented by the following general formula (1) to the synthetic resin.

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group which may have one or more substituents,
X ¹ and X ² each independently represent a direct bond, an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a nitrogen atom or a sulfur atom, and are optionally adjacent to each other in the alkylene group having 1 to 8 carbon atoms. Oxygen atom, nitrogen atom or sulfur atom may be present between carbon atoms,
R ² represents —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —,
n represents a number of 1 to 10000.

The flame retardant of the present invention has excellent heat resistance, and when added to a synthetic resin, particularly a polyester resin, the flame retardancy of the synthetic resin can be significantly 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 described.
The flame retardant of the present invention contains at least one compound represented by the following general formula (1).

In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group which may have one or more substituents,
X ¹ and X ² each independently represent a direct bond, an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a nitrogen atom or a sulfur atom, and are optionally adjacent to each other in the alkylene group having 1 to 8 carbon atoms. Oxygen atom, nitrogen atom or sulfur atom may be present between carbon atoms,
R ² represents —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —,
n represents a number of 1 to 10000.

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 hydrocarbon group having 3 to 20 carbon atoms. Heterocyclic groups are mentioned. The aromatic hydrocarbon ring group having 6 to 20 carbon atoms may be a single ring or a condensed ring. Examples of the monocyclic aromatic hydrocarbon ring group include a phenyl group, a biphenyl group and a terphenyl group. Examples of the condensed ring aromatic hydrocarbon ring group include a naphthyl group, a fluoryl group and a pyrenyl group. Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include furanyl group, thiophenyl group, chromenyl group, benzothiophenyl group, bifuranyl group, terfuranyl group, bithiophenyl group, terthiophenyl group, selenophenyl group, and biphenyl group. Examples thereof include a selenophenyl group and a terselenophenyl group. Among these aromatic groups, R ¹ and R ³ are preferably aromatic hydrocarbon ring groups having 6 to 20 carbon atoms from the viewpoint of flame retardancy and compatibility with resins, and monocyclic aromatic hydrocarbon groups are preferred. A hydrogen ring group is more preferred, and a phenyl group is even more preferred. The aromatic group preferably has 6 to 10 carbon atoms.

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-like or cyclic. The chain alkyl group may be linear or branched. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group and a 1-octyl group. Examples of the branched alkyl group include an iso-propyl group, a sec-butyl group, a tert-butyl group, an iso-butyl group, an iso-amyl group, a tert-amyl group, a 2-hexyl group, a 3-hexyl group, Examples thereof include a 2-heptyl group, a 3-heptyl group, an iso-heptyl group, a tert-heptyl group, an iso-octyl group and a tert-octyl group. Examples of the cyclic alkyl group include a cyclohexyl group and a 1-methylcyclohexyl group. In the present invention, a linear alkyl group is preferable as the substituent from the viewpoint of flame retardancy and resin compatibility. The linear alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 or 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 with one of the above alkyl groups, the substitution position of the alkyl group is an ortho position, a meta position and Any of the para positions may be used, and the para position is particularly preferable. When R ¹ and / or R ³ in the general formula (1) is a phenyl group and the phenyl group is substituted with two alkyl groups as described above, the substituted position of the alkyl group is ortho, meta and It may be in any of the para positions, and the meta position is particularly preferable.

Examples of the alkoxy group having 1 to 8 carbon atoms include a group in which an oxygen atom is bonded to the terminal of the alkyl group having 1 to 8 carbon atoms. When R ¹ and / or R ³ in the general formula (1) is a phenyl group and the phenyl group is substituted with one of the above alkoxy groups, the substitution position of the alkoxy group is an ortho position, a meta position or a para position. Any of the positions may be used, and the para position is particularly preferable. When R ¹ and / or R ³ in the general formula (1) is a phenyl group and the phenyl group is substituted with two alkoxy groups as described above, the substitution position of the alkoxy group is an ortho position, a meta position or It may be in any of the para positions, and the meta position is particularly preferable.

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 group, 2-methyl- 1,3-butanediyl group, 2,4-pentanediyl group, 1,4-pentanediyl group, 3-methyl-1,4-butanediyl group, 2-methyl-1,4-pentanediyl group, pentamethylene group, hexamethylene group , Heptamethylene group, octamethylene group and the like. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 carbon atom, from the viewpoint of flame retardancy and compatibility with resins. Particularly preferred is methylene.

An oxygen atom, a nitrogen atom or a sulfur atom may be present between any adjacent carbon atoms in the alkylene group. In the compound represented by the general formula (1), oxygen atom, nitrogen atom or sulfur atom is selected from oxygen atom, nitrogen atom or sulfur atom at one or more positions of the alkylene group, provided that oxygen atom, nitrogen atom or sulfur atom are not adjacent to each other. There may be one or more types of heteroatoms interposed.

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

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 of 1 to 10000, preferably 3 to 10000, more preferably 5 to 10000, and 10 to 10000 is heat resistance, flame retardancy and compatibility. From the viewpoint of. The flame retardant of the present invention may be composed of only a single compound in which n is one type, or may be a mixture of compounds in which n is two or more different types. When a mixture of two or more different n's is used as the flame retardant of the present invention, the number of n may be represented 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 similar to the known method for producing pentaerythritol phosphonate. For example, a compound represented by the following general formula (A) and a compound represented by the general formula (B-1) or (B-2) are used as starting materials, and these are heated in a solvent under heating. The reaction is carried out and the polymerization is carried out. As the solvent, for example, toluene, xylene, monochlorobenzene, dichlorobenzene, propylene carbonate, ethylene carbonate, sulfolane, diglyme or the like can be used. To stop the polymerization, the compound represented by the general formula (C) may be added to the reaction system.

In formula (A), R ^a and R ^b are each independently a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, an iso-butyl group, or the like. Represents an alkyl group having 1 to 4 carbon atoms.

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

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

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

Examples of the compound of the present invention represented by the general formula (1) used as a flame retardant include the following No. 1 to No. Although the compound group represented by 4 is mentioned, it is not particularly limited to these and derivatives thereof can also be used as long as they are represented by the general formula (1). Among these, No. 1 is preferable in terms of heat resistance and flame retardancy. Compound 1 is preferred.

No. In 1, n represents a number of 1 to 10000.

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

No. In 3, n represents a number from 1 to 10000.

No. In 4, n represents a number from 1 to 10000.

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

Next, the flame retardant composition of the present invention will be described.
The flame retardant composition of the present invention contains a 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 type of the compound represented by the above general formula (1) or may contain two or more types thereof. By using the flame retardant of the present invention in combination with one or more kinds of phosphate compounds, it is possible to exert an effect that excellent flame retardancy can be imparted to the synthetic resin.

Examples of the phosphate compound used in the flame retardant composition of the present invention include phosphates such as melamine phosphate and piperazine phosphate; polyphosphates such as ammonium polyphosphate, melamine polyphosphate and piperazine polyphosphate; ortholine. Orthophosphates such as melamine acid and piperazine orthophosphate; pyrophosphate salts such as ammonium pyrophosphate, melamine pyrophosphate and piperazine pyrophosphate; calcium phosphate; magnesium phosphate and derivatives thereof. The flame retardant composition of the present invention may contain only one kind of these phosphate compounds or may contain two or more kinds thereof. The phosphate compound used in the flame retardant composition of the present invention preferably contains a pyrophosphate from the viewpoint of flame retardancy and processability.

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

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

As the above-mentioned other additives, it is possible to use known additives used in the technical field to which the present invention belongs, as long as the effects of the present invention are not impaired, and the known additives can be added in any amount. It can be blended. Examples of the other additives include, for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, hindered amine light stabilizers, ultraviolet absorbers, plasticizers, and nucleating agents. Other than the flame retardant of the present invention, one or more selected from flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, metal soaps, antistatic agents, pigments and dyes are used.
These other additives may be blended directly into the flame retardant composition, or when blended into the synthetic resin, they may be blended into the synthetic resin separately from the flame retardant composition.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-). Hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3 -Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidene bis (4,6-ditert-butylphenol), 2,2'-ethylidene bis (4,6- Di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy- 3-tert-Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6 Trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4] -Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- {3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propanoyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and triethylene Examples thereof include glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. These phenolic antioxidants may be used alone or in combination of two or more. The content of the phenolic antioxidant in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, but is included in the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.8 part by mass, based on 100 parts by mass of the synthetic resin.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyl phenyl phosphite, Diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, Bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylfe Rubis (nonylphenyl) phosphite, poly (dipropyleneglycol) phenylphosphite, tetraphenyldipropylglycol diphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl Phenyl] phosphite, tri (decyl) phosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl C10) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) 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) ethylphosphite, tetra (tridecyl) isopropylidene diphe Nol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4) -Hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecylphosphite, 2,2′-methylenebis ( 4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-me Renbis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4'-butylidene bis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphespiro [5,5] undecane, 2 , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidene diph Nord C12-15 alcohol phosphite, and the like. These phosphorus-based antioxidants may be used alone or in combination of two or more. The content of the phosphorus-based antioxidant in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, but is included in the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.8 part by mass, based on 100 parts by mass of the synthetic resin.

Examples of the thioether antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butyl. Phenyl) sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipronate Pionate, lauryl / stearyl thiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl-p-cresol), distearyl- Disulfide can be mentioned. These thioether antioxidants may be used alone or in combination of two or more. The content of the thioether-based antioxidant in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, but is included in the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 5 parts by mass, based on 100 parts by mass of the synthetic resin.

Examples of the hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,2. 6,6-Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,2 6,6-Tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl- -Piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,3 5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinole / diethyl succinate polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6 , 6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N -Butyl N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12- Tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12 -Tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6- Ile] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 -Yl] aminoundecane, bis {4- (1-octyloxy-2,2 , 6,6-Tetramethyl) piperidyl} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, CINBA Specialty Chemicals TINUVIN NOR 371 Etc. These hindered amine light stabilizers may be used alone or in combination of two or more. The content of these hindered amine-based light stabilizers can be set within a range that does not impair the effects of the present invention, but with respect to 100 parts by mass of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. Therefore, the amount of 0.001 to 10 parts by mass is preferable, and the amount of 0.005 to 1 part by mass is more preferable.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methyl) Phenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert) -Octyl-6-benzotriazolylphenol), 2- (2-hydr) Polyethylene glycol ester of xy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2- Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2 -[2-Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole , 2- [2-hydroxy 3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [ 2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2 2- (2 such as-[2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole and 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole -Hydroxyphenyl) benzotriazo Phenylsalicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4- Hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert- Benzates such as butyl-4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2- Ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'- Substituted oxanilides such as decyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various Examples thereof include metal salts or metal chelates, particularly nickel or chromium salts, or chelates. These ultraviolet absorbers may be used alone or in combination of two or more. The content of the ultraviolet absorber in the flame retardant composition of the present invention can be within a range that does not impair the effects of the present invention, but a synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, relative to 100 parts by mass.

Examples of the plasticizer include phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, Trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate Phosphate type plasticizers such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Polyhydric alcohols such as 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, etc. Polyester plasticizers other than the present invention using dibasic acid and, if necessary, monohydric alcohol, monocarboxylic acid (acetic acid, aromatic acid, etc.) as a stopper; epoxidized soybean oil, epoxidized Flaxseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil Oil, epoxidized safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearic acid stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall Epoxy plasticizers such as oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexylmethyl, epoxycyclohexanecarboxylate, and others, Sebacic acid plasticizers such as tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, di-2-ethylhexyl sebacate (DOS), dibutyl sebacate (DBS) Agent, stearic acid plasticizer, citric acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer, polyhydric alcohol aromatic acid ester plasticizer (trimethylolpropane tribenzoate, etc.), etc. Is mentioned. Preferred examples include polyester plasticizers other than the present invention, phthalate plasticizers, trimellitate plasticizers, adipate plasticizers, sebacic acid plasticizers, and epoxy plasticizers. These plasticizers may be used alone or in combination of two or more. The content of the plasticizer 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, but the synthetic resin 100 contained in the synthetic resin composition containing the flame retardant composition of the present invention An amount of 1 to 90 parts by mass is preferable, and an amount of 10 to 80 parts by mass is more preferable.

Examples of the nucleating agent include carboxylic acids such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate. Metal salts, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-) Phosphoric acid ester metal salts such as di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and polyhydric alcohol derivatives such as bis (dimethylbenzylidene) sorbitol, N, N ', N " Tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide (RIKACLEAR PC1), N, N ', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N'-dicyclohexyl- Examples thereof include amide compounds such as naphthalene dicarboxamide and 1,3,5-tri (dimethylisopropoylamino) benzene. These nucleating agents may be used alone or in combination of two or more. The content of the nucleating agent in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, but a synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is preferably 1 to 90 parts by mass, more preferably 10 to 80 parts by mass, based on 100 parts by mass.

Examples of the other flame retardant include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1- Methylethylidene) -4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade names "ADEKA STAB FP-500", "ADEKA STAB FP-600" manufactured by ADEKA CORPORATION. Aromatic phosphate ester of "Adeka Stab FP-800", divinyl phenylphosphonate, diallyl phenylphosphonate, phosphonate ester such as phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, di Phosphinic acid esters such as methyl phenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresylphosphazene, red phosphorus Such as phosphorus-based flame retardants, magnesium hydroxide, metal hydroxides such as aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromo) Phenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated Phenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate , Pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. These flame retardants may be used alone or in combination of two or more. The content of these flame retardants in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, a synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is preferably 1 to 90 parts by mass, more preferably 3 to 80 parts by mass, based on 100 parts by mass.

The above flame retardant aids include inorganic flame retardant aids and organic flame retardant aids. Examples of the inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, and surface-treated products thereof. For example, 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 Co., Ltd.) and the like. Examples of the organic flame retardant aid include pentaerythritol, dipentaerythritol, and the like. These flame retardant aids may be used alone or in combination of two or more. The content of the flame retardant aid 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, but the synthetic resin composition containing the flame retardant composition of the present invention contains a synthetic resin composition. The amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the resin.

Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmititate. , Sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide and the like. These lubricants may be used alone or in combination of two or more. The content of the lubricant 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, but 100 mass of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. An amount of 0.01 to 10 parts by mass is preferable, and an amount of 0.03 to 1 part by mass is more preferable.

Examples of the filler 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, clay, Dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, etc. can be mentioned, and the particle diameter (fiber diameter or fiber length and aspect ratio in the fibrous state) is appropriately selected and used. be able to. The filler may be surface-treated if necessary. These fillers may be used alone or in combination of two or more. The content of the filler 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, but the synthetic resin 100 included in the synthetic resin composition containing the flame retardant composition of the present invention An amount of 0.01 to 90 parts by mass is preferable, an amount of 0.1 to 50 parts by mass is more preferable, and an amount of 5 to 40 parts by mass is further preferable. Among the above-mentioned fillers, it is particularly preferable to contain glass fibers. When the flame retardant composition of the present invention contains glass fiber, the content of the glass fiber is 100 parts by mass of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention from the viewpoint of processability. On the other hand, an amount of 10 to 40 parts by mass is preferable.

Examples of the hydrotalcites are complex salt compounds composed of magnesium, aluminum, hydroxyl group, carbonic acid group and arbitrary crystal water known as natural products or synthetic products, and a part of magnesium or aluminum is alkali metal or zinc. Examples thereof include those substituted with other metals and those substituted with hydroxyl groups and carbonic acid groups with other anion groups. Specifically, for example, the metal of hydrotalcite represented by the following general formula (2) is alkali. The thing substituted with the metal is mentioned. Further, water of crystallization may be dehydrated, higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salts, organic sulfonic acid metal salts such as dodecylbenzenesulfonic acid alkali metal salts, higher fatty acids. It may be coated with amide, higher fatty acid ester or wax. These may be natural products or synthetic products, and can be used without being limited by the crystal structure, crystal particles and the like. These hydrotalcites may be used alone or in combination of two or more. The content of hydrotalcites 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, but is not limited to the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.01 to 90 parts by mass, more preferably 0.1 to 50 parts by mass, still more preferably 5 to 40 parts by mass, based on 100 parts by mass of the resin.

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 alone or in combination of two or more. The content of the metal soap in the flame retardant composition of the present invention can be blended within a range that does not impair the effects of the present invention, but a synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 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 adduct, polyethylene glycol fatty acid ester, anionic alkyl Anionic antistatic agents such as sulfonates, higher alcohol sulfuric acid ester salts, higher alcohol ethylene oxide adduct sulfuric acid ester salts, and higher alcohol ethylene oxide adduct phosphoric acid ester salts; polyhydric alcohol fatty acid esters, polyglycol phosphoric acid esters, polyoxy Nonionic antistatic agents such as ethylene alkyl allyl ether; amphoteric alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric antistatic agents such as imidazoline type amphoteric active agents. These antistatic agents may be used alone or in combination of two or more. The content of the antistatic agent in the flame retardant composition of the present invention can be within the range that does not impair the effects of the present invention, but a synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention The amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, relative to 100 parts by mass.

As the pigment, for example, a commercially available pigment may be used, and for example, 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 and the like. These pigments may be used alone or in combination of two or more. The content of the pigment 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, but 100 mass% of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.001 to 5 parts by mass, and more preferably 0.003 to 3 parts by mass with respect to parts.

Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes. , Dyes such as phthalocyanine dyes and cyanine dyes. These dyes may be used alone or in combination of two or more. The content of the pigment 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, but 100 mass% of the synthetic resin contained in the synthetic resin composition containing the flame retardant composition of the present invention. The amount is preferably 0.001 to 5 parts by mass, and more preferably 0.003 to 3 parts by mass with respect to parts.

Next, the synthetic resin composition of the present invention will be described.
The synthetic resin composition of the present invention comprises a 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 to 50 parts by mass with respect to 100 parts by mass of the synthetic resin, and from the viewpoint of flame retardancy, it is preferably 0.05 to The amount is 45 parts by mass, more preferably 1 to 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 be insufficient, and if it is more than 50 parts by mass, the physical properties of the synthetic resin may be impaired.

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 to 100 parts by mass with respect to 100 parts by mass of the synthetic resin, and preferably 0.05 from the viewpoint of flame retardancy. To 95 parts by mass, more preferably 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 retarding effect may be insufficient, and if it is more than 100 parts by mass, the physical properties of the synthetic resin may be impaired.

Examples of the synthetic resin used in the synthetic resin composition of the present invention include a thermoplastic resin and a thermosetting resin, and the thermoplastic resin can be preferably used.
Examples of the thermoplastic resin include polyvinyl chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl acetate resin, polyurethane resin, cellulosic resin, acrylic resin, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene). -Styrene) resin, fluorine resin, thermoplastic elastomer, polyamide resin, polyacetal resin, polycarbonate resin, modified polyphenylene ether resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, polylactic acid resin), cyclic polyolefin resin , Polyphenylene sulfide resin and the like. These synthetic resins may be used alone or in combination of two or more kinds. Among these synthetic resins, a polyester resin or a polyamide resin is preferable, a polyester resin is more preferable, and a polybutylene terephthalate resin (PBT resin) is particularly 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 is used, a glycol having 2 to 10 carbon atoms as a glycol component, another divalent alcohol, or Examples thereof include saturated polyester resins obtained by using such derivatives having ester forming ability. Among these, polyalkylene terephthalate resin is preferable. Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin.

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; alicyclic rings such as bis (aminocyclohexyl) C _1-3 alkanes. Alicyclic polyamides obtained from aromatic diamines and 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) , Nonamethylenediamine, etc.); polyamides obtained from aromatic and aliphatic dicarboxylic acids (eg, terephthalic acid and adipic acid) and aliphatic diamines (eg, hexamethylenediamine), 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, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, at an arbitrary addition amount, Other antioxidants, hindered amine light stabilizers, ultraviolet absorbers, plasticizers, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, metal soaps, antistatic agents, pigments, Dyes) and other known resin additives can be added. 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 for blending the flame retardant of the present invention or the flame retardant composition of the present invention with a synthetic resin is not particularly limited, and a known method can be adopted. Specific mixing methods include a method of mixing with a usual blender, a mixer, etc., a method of melt-kneading with 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. Specific molding methods include extrusion molding, injection molding, stretched film molding, blow molding and the like, and these molding methods can be carried out 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 a sheet shape, a film shape, and a special shape.
The use of the obtained molded article is not particularly limited, but examples thereof include food containers, electronic parts, automobile parts, medical prize materials, film / sheet materials, fiber materials, optical materials, paint resins, ink resins, toner resins. , Resins for adhesives, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[Example 1] (Synthesis of flame retardant compound No. 1)
In the flask, 54.4 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphospyro [5,5] undecane and 24.42 g (0.13 mol of 1,2-dibromoethane) were added. ) And 150 ml of sulfolane were added and the reaction was allowed to proceed at 150 ° C. for 10 hours. 66.71 g (0.39 mol) of benzyl bromide was further added to the flask, and the reaction was allowed to proceed at 150 ° C for 2 hours. After the reaction, the reaction solution was cooled to room temperature. The reaction liquid cooled to room temperature was transferred to a beaker, 300 ml of acetone was added, and filtration was performed. This washing operation was repeated three times. The residue was dried in a vacuum oven at 150 ° C for 5 hours. A white powder was obtained. The yield was 32.9 g (80.5%). The obtained compound was identified by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). The obtained compound No. ¹ H-NMR and ³¹ P-NMR of 1 were as follows. The obtained compound No. The average polymerization degree n of 1 was 47 calculated from 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)
In the flask, 54.4 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphospyro [5,5] undecane and 26.25 g (0.13 mol) of 1,3-dibromopropane were placed. ) And 150 ml of sulfolane were added and the reaction was allowed to proceed at 150 ° C. for 10 hours. 66.71 g (0.39 mol) of benzyl bromide was further added to the flask, and the reaction was allowed to proceed at 150 ° C for 2 hours. After the reaction, the reaction solution was cooled to room temperature. The reaction liquid cooled to room temperature was transferred to a beaker, 300 ml of acetone was added, and filtration was performed. This washing operation was repeated three times. The residue was dried in a vacuum oven at 150 ° C for 5 hours. A white powder was obtained. The yield was 34.4 g (75.6%). The obtained compound was identified by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). The obtained compound No. ¹ H-NMR and ³¹ P-NMR of 2 were as follows. The obtained compound No. For 2, the average degree of polymerization n was calculated to be 50 from 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)
Comparative compound A shown below was synthesized by the method described below.

In the flask, 54.3 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphospyro [5,5] undecane and 28.10 g (0.13 mol) of 1,4-dibromobutane were added. ) 150 ml of ethylene carbonate was added, and the reaction was allowed to proceed 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 allowed to proceed at 150 ° C for 2 hours. Purification was performed using compound No. The procedure was the same as that used for the synthesis of 1. The yield was 33.71 g (71.2%). The compound thus obtained was designated as Comparative Compound A. The obtained compound was identified by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound A were as follows. The average degree of polymerization n of Comparative Compound A was calculated to be 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)
Comparative compound B shown below was synthesized by the method described below.

In the flask, 54.3 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa-3,9-diphospyro [5,5] undecane and 28.10 g (0.13 mol) of 1,4-dibromobutane were added. ) 150 ml of propylene carbonate was added, and the reaction was allowed to proceed at 150 ° C for 7 hours. 53.50 g (0.39 mol) of bromobutane was further added to the flask, and the reaction was allowed to proceed for 8 hours under reflux of bromobutane. Purification was performed using compound No. The procedure was the same as that used for the synthesis of 1. The yield was 27.12 g (65.5%). The compound thus obtained was designated as Comparative Compound B. The identification of the comparative compound B was performed by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound B were as follows. The average degree of polymerization n of Comparative Compound B was calculated to be 45 from 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)
Comparative compound C shown below was synthesized by the method described below.

In the flask, 54.4 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa3,9-diphospyro [5,5] undecane and 34.3 g of α, α′-dibromo-p-xylene were placed. (0.13 mol) and 150 ml of diethyl oxalate were added, and the reaction was allowed to proceed at 150 ° C for 5 hours. After the reaction, the reaction solution was cooled to room temperature. Further, 54.71 g (0.40 mol) of bromobutane was added to the flask, the temperature was raised until the bromobutane was refluxed, and the reaction was allowed to proceed for 8 hours. After that, purification was performed using compound No. The procedure was the same as that used for the synthesis of 1. The yield was 39.24 (68.2%). The compound thus obtained was designated as Comparative Compound C. The obtained compound was identified by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound C were as follows. The average degree of polymerization n of Comparative Compound C was calculated to be 48 from ¹ H-NMR.

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)
Comparative compound D shown below was synthesized by the method described below.

To the flask was added 57.34 g (0.16 mol) of 3,9-dibutoxy-2,4,8,10-tetraoxa3,9-diphospyro [5,5] undecane and 125.6 g (0.80 mol) of benzyl bromide. The reaction was allowed to proceed at 150 ° C for 3 hours. After completion of the reaction, benzyl bromide was distilled off under reduced pressure. The obtained powder was dispersed in 50 g of acetone, stirred for 30 minutes, and then the dispersion was filtered. This washing operation was repeated three times. It was dried under reduced pressure at 150 ° C. for 5 hours. The yield was 55.87 g (80.1%). The obtained compound was designated as Comparative Compound D. The identification of the comparative compound D was performed by ¹ H-NMR and ³¹ P-NMR (measurement device: AVANCE III HD NMR Spectrometer, manufactured by BRUKER Corporation). ¹ H-NMR and ³¹ P-NMR of the obtained comparative compound D were 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. Table 1 shows the results.

[Heat resistance evaluation method]
Using a thermogravimetric / differential thermal analyzer Thermo plus EVO (manufactured by Rigaku Corporation), the compound No. 1 and 2 and comparative compounds A to D were heated from 30 ° C. to 450 ° C. at a heating rate of 10 ° C./min under a flow of 200 ml / min of nitrogen, and 1% weight and 5% weight loss temperatures were measured.

As is apparent from Table 1, the compound No. synthesized in Example 1 and included in the flame retardant of the present invention. No. 1 had better heat resistance than Comparative Compounds A to D synthesized in Comparative Examples 1 to 4.
In addition, the compound No. included in the flame retardant of the present invention synthesized in Example 2 was used. No. 2 had excellent heat resistance almost equal to those of Comparative Compounds A to D synthesized in Comparative Examples 1 to 4.

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

[Flame Retardancy (UL-94V) Evaluation Method]
The synthetic resin composition was pressed for 15 minutes at 280 ° C. and 5 to 15 MPa to obtain a test piece for evaluating the flame retardancy test having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm. The obtained test piece is compliant with ISO1210 and 20 mm vertical burning test (UL-94V), and the test piece is kept vertical. The flame is removed from the burner by indirect flame at the lower end for 10 seconds. The time for extinguishing the ignited fire was measured. Next, when the fire was extinguished, the second flame contact was performed for 10 seconds, and the time for extinguishing the ignited fire was measured in the same manner as the first time. Also, whether or not the cotton under the test piece ignites depending on the type of fire that dropped was evaluated at the same time. The combustion rank was set according to the UL-94V standard based on the first and second burning times, the presence or absence of cotton ignition. The highest combustion rank is V-0, and the flame retardancy decreases as V-1 and V-2.

As is clear from Table 2, the synthetic resin compositions of Examples 5 and 10 using the flame retardant (flame retardant resin composition) of the present invention are the same as those of Comparative Examples A to D except that Comparative Compounds A to D are used. It has good flame retardancy as compared with the synthetic resin compositions of Comparative Examples 5 to 8 having the same composition as 5 and 10. From this, it is clear that the flame retardant (flame retardant resin composition) of the present invention can provide a synthetic resin having good flame retardancy.

Claims (11)

1. A flame retardant containing a compound represented by the following general formula (1).
   

   

   In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group which may have one or more substituents,
   X ¹ and X ² each independently represent a direct bond, an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a nitrogen atom or a sulfur atom, and are optionally adjacent to each other in the alkylene group having 1 to 8 carbon atoms. Oxygen atom, nitrogen atom or sulfur atom may be present between carbon atoms,
   R ² represents —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —,
   n represents a number of 1 to 10000.
2. The flame retardant according to claim 1, wherein in the general formula (1), R ¹ and R ³ are each independently a monocyclic aromatic hydrocarbon ring group.
3. The flame retardant according to claim 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.
4. A flame retardant composition containing the flame retardant according to any one of claims 1 to 3 and a phosphate compound.
5. The flame retardant composition according to claim 4, wherein the phosphate compound is pyrophosphate.
6. The flame retardant composition according to claim 4 or 5, wherein the mass ratio of the flame retardant to the phosphate compound is 9: 1 to 1: 9 in the former case and the latter case.
7. A synthetic resin composition containing 0.01 to 50 parts by mass of the flame retardant according to any one of claims 1 to 3 with respect to 100 parts by mass of the synthetic resin.
8. A synthetic resin composition, and a synthetic resin composition containing 0.01 to 100 parts by mass of the flame retardant composition according to any one of claims 4 to 6 with respect to 100 parts by mass of the synthetic resin.
9. The synthetic resin composition according to claim 7 or 8, wherein the synthetic resin is one or more selected from the group consisting of polyester resins and polyamide resins.
10. A molded product of the synthetic resin composition according to any one of claims 7 to 9.
11. A method for flame-retarding a synthetic resin, comprising adding a compound represented by the following general formula (1) to the synthetic resin.
    

    

    In the general formula (1), R ¹ and R ³ each independently represent a monovalent aromatic group which may have one or more substituents,
    X ¹ and X ² each independently represent a direct bond, an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a nitrogen atom or a sulfur atom, and are optionally adjacent to each other in the alkylene group having 1 to 8 carbon atoms. Oxygen atom, nitrogen atom or sulfur atom may be present between carbon atoms,
    R ² represents —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —,
    n represents a number of 1 to 10000.