JP2003082159A - Flame retardant for synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant for a synthetic resin comprising an aromatic phosphate compound which is solid when used in addition to a synthetic resin and does not bleed. SOLUTION: In the aromatic phosphate compound represented by the following general formula (I), the content ratio of the aromatic phosphate compound in which n is 1 is 92 to 99.5% by mass,
The content of at least one aromatic phosphate compound in which n is 0 and / or 2 to 10 (n is an aromatic phosphate compound other than 1) is 0.5 to 8% by mass, and the solid content at 40 ° C. Is a synthetic tree flame retardant. Embedded image

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant for a synthetic resin, which comprises an aromatic phosphate compound having a specific structure and can be used in a solid state.
And a solid flame retardant for a synthetic resin comprising an aromatic phosphate compound having a bisphenol A residue and a phenol residue.

[0002]

Conventionally, as a flame retardant for imparting flame retardancy to a synthetic resin composition, a system in which a halogen-based organic compound and antimony trioxide are combined has been used. A halogen-free material is required due to contamination of a molding die with organic organic compounds, toxic gas generated during combustion and incineration, and environmental problems. Various aromatic phosphate compounds are used as flame retardants for halogen-free synthetic resins.

The properties required as a flame retardant for a synthetic resin are that it does not impair the physical properties of the synthetic resin when added and used, it has excellent heat resistance and is not colored, it has excellent compatibility with the synthetic resin and does not bleed. As the aromatic phosphate compound satisfying these, a flame retardant composed of an aromatic phosphate compound having a bisphenol A residue and a phenol residue is particularly disclosed in Japanese Patent No. 3043694, Japanese Patent Application Laid-Open No. 5-186681, and Japanese Patent Application Laid-Open No. 7-186681. -258
539, JP 9-249768, and JP 2
000-319494, JP 2000-3194A.
It is reported in Japanese Patent Publication No. 95.

The above-mentioned flame retardant comprising a bisphenol A residue and an aromatic phosphate compound having a phenol residue is industrially produced by an esterification reaction of a phosphorus oxyhalide compound such as phosphorus oxychloride with bisphenol A and phenol. The obtained liquid is a liquid containing triphenyl phosphate and an oligomer component. This has a problem in that, when it is added to a synthetic resin, equipment and complicated work for homogeneously mixing a liquid (flame retardant) and a solid (synthetic resin and other additives) are involved.

A solid flame retardant composed of an aromatic phosphate compound is described in Japanese Patent No. 2815328, but it has a bisphenol A residue and a lower alkylphenol residue, and solidification is more difficult than this. There is no description about the aromatic phosphate compound having bisphenol A residue and phenol residue. Also, in ANTEC'98 / 2875-2879, a solid flame retardant composed of an aromatic phosphate compound having a bisphenol A residue and a phenol residue is described. Although it is a solid, it contains a large amount of low-molecular impurities such as triphenyl phosphate, so that it is not satisfactory in terms of mold contamination during processing and molding of bleed and synthetic resin.

Accordingly, it is an object of the present invention to provide a flame retardant for a synthetic resin, which is a solid and does not bleed when it is added to the synthetic resin and is composed of an aromatic phosphate compound.

[0007]

As a result of repeated studies, the present inventors have found that a flame retardant for a synthetic resin having a specific structure and composition can solve the above-mentioned problems, and arrived at the present invention. .

That is, in the present invention, in the aromatic phosphate compound represented by the following general formula (I), the content ratio of the aromatic phosphate compound in which n is 1 is 92 to 99.5.
%, And n is 0 and / or at least one aromatic phosphate compound selected from 2 to 10 (n is 1
Aromatic phosphate compounds other than 0.5)
A flame retardant for a synthetic resin, which is -8% by mass and is solid at 40 ° C.

[0009]

[Chemical 2]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The first feature of the flame retardant for synthetic resins of the present invention is that it is solid at a temperature of 40 ° C. This is because if it is solid at this temperature, it can be used in a solid state when it is usually added to a synthetic resin. The flame retardant for synthetic resins of the present invention is not limited by the melting point as long as it is solid at 40 ° C. The melting point depends on factors such as the composition and the solidification (crystallization) step, and some melting points using differential thermal analysis do not show a clear melting point, but some melting points do not show a clear melting point. When it is liquefied by being exposed to a temperature sufficient for dissolution, it may be difficult to return it to a solid.

Therefore, those having a melting point are preferable, and those having the top of the endothermic peak of the melting point in the range of 55 to 78 ° C. in the melting point measurement using the differential thermal analysis are more preferable, and those in the range of 60 ° C. to 78 ° C. It is more preferable that what is present is difficult to block when it is made into a powder state.

The second feature of the flame retardant for synthetic resin of the present invention is that the content of the aromatic phosphate compound in which n is 1 in the general formula (I) is in the range of 92 to 99.5% by mass. Especially. This is a range in which it is easy to make the flame retardant into a solid, and further, a range in which the flame retardant has properties suitable as a flame retardant for synthetic resins. Further, in the above general formula (I), the content ratio of n is 0 and / or at least one kind of aromatic phosphate compound selected from 2 to 10 (aromatic phosphate compound other than n being 1) is 0.
It is necessary to be 5 to 8 mass%. It is known that when the content of triphenyl phosphate, which is an aromatic phosphate compound in which n is 0, is large, problems such as deterioration of heat resistance, contamination of processing machines and bleeding occur, and oligomers in which n is 2 or more. When the amount of the component is large, the melting point of the flame retardant may decrease, and when added to the synthetic resin, it may affect the physical properties such as lowering the softening point of the synthetic resin.

When the content of the aromatic phosphate compound (triphenyl phosphate) in which n is 0 is 3% by mass or less, deterioration of heat resistance and bleeding are not observed, so 3% by mass or less is preferable.

For oligomer components in which n is 2 or more,
The larger n is, the smaller the phosphorus concentration is, and the softening point of the synthetic resin is further lowered. Therefore, the total content of the aromatic phosphate compounds having n of 3 to 10 is preferably 1% by mass or less.

In the flame retardant for synthetic resin of the present invention, the manufacturing method is not particularly limited by the synthesizing method, the solidifying method and the like, and well-known general methods can be used. Generally, it is synthesized by an esterification reaction of phosphorus oxyhalide with bisphenol A and phenol, and the esterification reaction is carried out in the presence of a catalyst or without a catalyst. As catalysts, sulfuric acid, Bronsted acids such as p-toluenesulfonic acid, and aluminum chloride,
Examples thereof include Lewis acids such as magnesium chloride, zinc chloride, ferric chloride and stannic chloride, onium salts, pyridines and inorganic salts.

As the above-mentioned synthetic method, a method for producing a monochlorodiphenyl ester derivative by ester reaction of phosphorus oxyhalide with phenol and reacting this with bisphenol A, esterification of phosphorus oxyhalide with bisphenol A Examples thereof include a method of producing a bisphenol A phosphoryl halide derivative by a reaction and reacting it with phenol, and a method of reacting phosphorus oxyhalide with bisphenol A and phenol at once.

Examples of the above-mentioned solidification method include solidification or crystallization by cooling, solidification or crystallization by solvent exchange, crystallization by seed crystals, solidification or crystallization by applying stress such as pressure or impact. However, these may be used in combination. Also,
After the solidification step, it may be pulverized, extruded, or processed into powder or granules by a disc pelleter or the like.

The flame retardant for synthetic resins of the present invention is not particularly limited in its application and can be used as a well-known general flame retardant for synthetic resins. As the synthetic resin, for example, low density polyethylene, linear low density polyethylene,
High density polyethylene, polypropylene, polybutene
1, α-olefin polymers such as poly-3-methylbutene and poly-3-methylpentene, or ethylene-vinyl acetate copolymers, polyolefin resins such as ethylene / propylene block or random copolymers, and copolymers thereof ; Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , Halogen-containing resins such as vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers;
Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyhexamethylene terephthalate; polystyrene, high impact polystyrene (HIPS), acrylonitrile butadiene styrene (ABS), polyethylene chloride acrylonitrile styrene (ACS), styrene acrylonitrile ( SAN), acrylonitrile butyl acrylate styrene (AAS), butadiene styrene, styrene maleic acid, styrene maleimide, ethylene propylene acrylonitrile styrene (AES), butadiene-methyl methacrylate styrene (MBS) and other styrene resins; polycarbonate, branched polycarbonate and other polycarbonates. -Based resin: polyhexamethylene adipamide (nylon 66), Li caprolactam (nylon 6)
Polyamide resin such as polyphenylene oxide (PP
O) resin, polyphenylene sulfone (PPS) resin,
Polyacetal (POM), petroleum resin, coumarone resin,
Examples of the thermoplastic resin include polyvinyl acetate resin, acrylic resin, and polymer alloy of polycarbonate and styrene resin. Further, thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, urethane resin, silicone resin and unsaturated polyester resin, natural rubber (NR), polyisoprene rubber (IR), styrene butadiene rubber (SBR), Polybutadiene rubber (B
R), ethylene-propylene-diene rubber (EPD
M), butyl rubber (IIR), chloroprene rubber, acrylonitrile butadiene rubber (NBR), silicone rubber, and other rubber-based polymer compounds, which are particularly suitable for thermoplastic resins. Among them, polyolefin-based resins, polycarbonate-based resins, It is more suitable for one type or two or more types of polymer alloys selected from polyester resins, polyphenylene oxide (PPO) resins, and styrene resins.

The amount of the flame retardant for synthetic resin of the present invention used is not particularly limited as long as the flame retardant effect is exhibited. If it is less than 3 parts by mass with respect to 100 parts by mass of the synthetic resin, the flame retardant effect may not be exhibited, and if it exceeds 25 parts by mass, the softening point may be lowered until it interferes with the use of the synthetic resin. -25 parts by mass is preferable, and
20 parts by mass is more preferred.

The synthetic resin flame retardant of the present invention may be used in combination with other additives when used in synthetic resins. Examples of other additives that can be used in combination include the following.

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate and 1,2,2,6,6-pentamethyl-4.
-Piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,
6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,2
6,6-tetramethyl-4-piperidyl) sebacate,
1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6-tetramethyl-
4-piperidyl methyl methacrylate, 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 , 6,6-Tetramethyl-4-piperidyl) .bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) -bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2 -(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-
Hydroxyethyl) -2,2,6,6-tetramethyl-
4-piperidinol / diethyl succinate polycondensate, 1,
6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane 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
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-triazine-6-
Il] -1,5,8,12-tetraazadodecane, 1,
6,11-Tris [2,4-bis (N-butyl-N-
(2,2,6,6-Tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- ( 1,2,2,6,6-Pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino]
Undecane, 3,9-bis [1,1-dimethyl-2-
[Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane and the like can be mentioned.

Examples of the ultraviolet absorber include 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 -Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzo Triazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3,5-dicumylphenyl) benzotriazole, 2,
2'-methylenebis (4-tertiary octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-
Polyethylene glycol ester of 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-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2-
2- (2-, such as [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole
Hydroxyphenyl) benzotriazoles; 2- (2
-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine , 2- (2-hydroxy-4
-Octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-
Hydroxy -4- (3-C ₁₂ ~C ₁₃ mixed alkoxy -2
-Hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4, 6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-
Dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxy) 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as phenyl) -1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary 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-butyl) Benzoates such as -4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 Substituted oxanilides such as'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
Cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, tris ( Nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl Phosphite, diphenyldecylphosphite, diphenyloctylphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, tributylphosphite, tris (2
-Ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexane dimethyl diphosphite, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,5-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-diamyl phenyl)] - isopropylidene Redenediphenyl phosphite, tetratridecyl
4,4'-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
・ 1,1,3-Tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphite,
Tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9
-Tetrakis tert-butyl dibenzo [d, f] [1,3,
2] Dioxaphosphepin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol-2,4,6-tri-tert-butylphenol monophosphite and the like can be mentioned.

Examples of phenolic antioxidants 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-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,
4'-thiobis (6-tert-butyl-m-cresol),
2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,
2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-)
Tert-Butylphenyl) butyric acid] glycol ester, 4,4′-butylidene bis (2,6-di-tert-butylphenol), 4,4′-butylidene bis (6-
Tert-butyl-3-methylphenol), 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'-ditert-butyl-
4'-hydroxyphenyl) propionate] methane,
2-tert-butyl-4-methyl-6- (2-acroyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy) -5-Methylhydrocinnamoyloxy) -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], etc. Can be mentioned.

Examples of sulfur antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). .Beta.-alkyl mercaptopropionic acid esters of the above polyols.

As the nucleating agent, 4-tert-butylbenzoic acid aluminum salt, carboxylic acid metal salt such as sodium adipate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2'-methylenebis ( Examples thereof include acidic phosphoric acid ester metal salts such as 4,6-di-tert-butylphenyl) phosphate, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, lithium benzoate, sodium benzoate, and aluminum benzoate.

As additives other than the above, metal deactivators, aluminum p-tert-butylbenzoate, dibenzylidene sorbitol, metallic soap, hydrotalcite,
Antistatic agents consisting of nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, anti-drip agents such as fluororesins, zirconium oxide, titanium oxide, metal oxides such as silicon oxide Flame retardant auxiliaries such as substances and phosphoric acid ester metal salts, lubricants such as ethylene bisalkyl amides, colorants such as dyes and pigments, processing aids and fillers can be used in combination.

Further, these additives may be contained in the flame retardant for synthetic resin of the present invention to form a composite additive such as a one-pack additive, within the range not impairing the object of the present invention.

[0030]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples, Evaluation Examples and Comparative Evaluation Examples. However, the present invention is not limited to the following examples.

Example 1 (Production of Flame Retardant A) A 200 ml reaction flask purged with nitrogen was charged with 2.0 mol of phosphorus oxychloride, 4.0 mol of phenol and 0.002 mol of magnesium chloride, and the mixture was heated to 80 ° C.
After stirring at 2, the hydrochloric acid generated at 110 ° C. was further stirred with nitrogen gas for 2 hours. By distilling and refining this, the front fraction and the rear fraction were cut by 10%, and diphenyl phosphate monochloride having a purity of 99% was obtained by GC analysis in a yield of 75%. A 200 ml reaction flask purged with nitrogen was charged with 0.5 mol of the diphenyl phosphate monochloride (intermediate) obtained above, 0.25 mol of bisphenol A, and 0.002 mol of magnesium chloride.
After stirring for 2 hours at 40 ° C, the hydrochloric acid generated at 140 ° C was stirred for 3 hours while purging with nitrogen gas, and xylene 30 was added.
g was added. This system was washed with dilute hydrochloric acid, dehydrated under reflux under reduced pressure, and then 1.9 g of triethyl orthoformate was added to give 1
The reaction was carried out at 20 ° C for 2 hours. After removing the solvent, the mixture was cooled to room temperature with stirring to obtain a flame retardant A with a yield of 97%. The components were analyzed using HPLC. The results are shown in Table 1.
Shown in.

Example 2 (Production of Flame Retardant B) Nitrogen-substituted 200 ml reaction flask was charged with 0.2 mol of bisphenol A, 0.002 mol of n-hexyltriphenylphosphonium bromide and 1.2 of phosphorus oxychloride. After charging 2 mol and stirring at 100 ° C. for 30 minutes, the hydrochloric acid generated at 100 to 110 ° C. was further stirred with nitrogen gas for 5 hours. Hydrochloric acid and unreacted phosphorus oxychloride are removed under reduced pressure at 100 ° C., cooled to 50 ° C., 0.002 mol of magnesium chloride and 0.8 mol of phenol are added, and the mixture is stirred at 120 ° C. for 30 minutes to generate further. 145 ° C while expelling hydrochloric acid with nitrogen gas
It was stirred for 5 hours. The pressure inside the system was reduced to 7,000 to 6000 Pa, low boiling impurities were distilled off, and then 25 g of xylene was added. This system was washed with dilute hydrochloric acid, treated with triethyl orthoformate and desolvated in the same manner as in Example 1 above to obtain a viscous liquid of a phosphate ester compound. This viscous liquid was recrystallized while cooling from a mixed solvent of toluene and hexane to obtain a flame retardant B with a yield of 88%. The components were analyzed using HPLC. The results are shown in Table 1.

Example 3 (Production of Flame Retardant C) Nitrogen-substituted 200 ml reaction flask was charged with 0.2 mol of bisphenol A, 0.002 mol of magnesium chloride and 1.25 mol of phosphorus oxychloride, After stirring at 0 ° C for 2 hours, the hydrochloric acid generated at 100 ° C was further stirred for 1 hour while purging with nitrogen gas.
Hydrochloric acid and unreacted phosphorus oxychloride were removed under reduced pressure at 100 ° C, and after cooling to 50 ° C, magnesium chloride 0.0
Add 02 mol and 0.9 mol of phenol, and add 3 at 120 ° C.
The mixture was stirred for 0 minutes, and the generated hydrochloric acid was chased with nitrogen gas, and the mixture was stirred at 145 ° C. for 5 hours. 6000 to 6 in the system
After reducing the pressure to 000 Pa to remove low boiling impurities, 25 g of xylene was added. This system was washed with dilute hydrochloric acid, treated with triethyl orthoformate and desolvated in the same manner as in Example 1 above to obtain a viscous liquid of a phosphate ester compound. This viscous liquid was recrystallized from a mixed solvent of toluene and hexane while cooling to obtain a flame retardant C with a yield of 86%. The components were analyzed using HPLC. The results are shown in Table 1.

Example 4 (Production of Flame Retardant D) A flame retardant D was obtained with a yield of 97% by the same operation as in Example 3 except for the solidification step. In the solidification step, a method was used in which 10% of the flame retardant A obtained above was added to the viscous liquid, and the mixture was stirred at room temperature until crystallized. The components of flame retardant D were analyzed using HPLC. The results are shown in Table 1.

Example 5 (Production of Flame Retardant E) By the same method as in Example 3 except that phosphorus oxychloride was changed to 1.0 mol, the yield was 97%.
Flame retardant E was obtained. The components were analyzed using HPLC. The results are shown in Table 1.

Comparative Example 1 (Production of Flame Retardant a) By the same method as in Example 4 except that the depressurizing removal time of phosphorus deoxychloride was halved.
Flame retardant a was obtained with a yield of 97%. About this HPLC
Were used to analyze the components. The results are shown in Table 1.

[0037]

[Table 1]

[Evaluation Examples 1-5 and Comparative Evaluation Examples 1-2] (Flame Retardancy and Bleed Evaluation) Polycarbonate (PC)
Resin (Brand name: Iupilon E-2000F, manufactured by Mitsubishi Engineering Plastics) 80 parts by mass and ABS resin (Brand name: Styrac 100, manufactured by Asahi Kasei Corporation) 20
Part by weight is mixed with a Henschel mixer and then placed in an oven for 12
After drying at 0 ° C. for 6 hours, the anti-drip agent polytetotefluoroethylene (trade name: Teflon (registered trademark)
6J, manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.) 0.1 part by mass, the flame retardant shown in Table 1 was dry blended, and pelletized at 260 ° C. using a single screw extruder. The obtained pellets were dried in an oven at 120 ° C for 6 hours, and then at a cylinder temperature of 260 ° C using an injection molding machine, a mold temperature of 100
A test piece of 5 inch × 1/2 inch × 1/16 inch was prepared at ° C. The obtained test piece was subjected to UL-94 test and bleed evaluation. The results are shown in Table 2. In addition,
In Comparative Evaluation Example 1, the flame retardant was not dry blended.

[0039]

[Table 2]

[0040]

INDUSTRIAL APPLICABILITY The present invention can provide a flame retardant for a synthetic resin, which is solid when added to a synthetic resin and is composed of an aromatic phosphate compound which does not bleed.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tetsuo Kamimoto             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. (72) Inventor Takafumi Fujii             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. F-term (reference) 4H028 AA35 BA06                 4H050 AA01 AA03 AB80 WA15 WA23                 4J002 AA011 EW046 FD136

Claims (3)

[Claims] 1. The aromatic phosphate compound represented by the following general formula (I), wherein the content of the aromatic phosphate compound in which n is 1 is 92 to 99.5% by mass,
The content ratio of at least one kind of aromatic phosphate compound (n is an aromatic phosphate compound other than 1) selected from 0 and / or 2 to 10 is 0.5 to 8% by mass and solid at 40 ° C. A flame retardant for synthetic resins. [Chemical 1] 2. In the above general formula (I), the content of the aromatic phosphate compound in which n is 0 is 3 mass% or less, and the total content of the aromatic phosphate compounds in which n is 3 to 10 is 1 mass. % Or less, and the flame retardant for synthetic resin according to claim 1. 3. In melting point measurement using differential thermal analysis,
The flame retardant for synthetic resin according to claim 1 or 2, wherein the top of the endothermic peak of the melting point is in the range of 55 to 78 ° C.