JP2011079950A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition satisfying a UL standard (V-0) using a flame retardant not including a halogen with a high solubility to a resin or a solvent without the risk of deteriorating the characteristics inherent to the resin such as mechanical characteristics and molding processability at the time of adding a resin without the risk of whitening, or hydrolysis. <P>SOLUTION: The flame-retardant resin composition includes a resin, and a flame retardant as a specific phosphorate-containing compound with the carbon atoms of a cyclohexane ring substituted by 6 phosphorate functional groups. Other phosphorate substituents each independently are a substituted or non-substituted alkyl group, a substituted or non-substituted cycloalkyl group, a substituted or non-substituted aryl group, or a substituted or non-substituted heterocyclic group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a flame retardant resin composition containing a flame retardant capable of imparting flame retardancy to a plastic material (resin material) by non-halogenation and non-antimony formation.

Plastic materials are widely used from features such as excellent moldability, mechanical properties, appearance, etc. to packages, building materials, fibers, household goods, electrical / electronic products, and the like. In particular, in applications such as electric / electronic products, office automation equipment, office equipment, communication equipment, and automobile-related members, it is necessary to make the resin flame-retardant due to problems such as heat generation and ignition of internal parts.
So far, flame retardant technology for parts made of plastic materials has been achieved by adding flame retardants such as halogen flame retardants, phosphorus flame retardants and inorganic flame retardants to make the base material flame retardant. We have satisfied the UL standard etc. mainly on the flame retardant method.

  Today, flame retardants are required to exert a flame retardant effect on all types of resins by adding a small amount. From this viewpoint, halogen flame retardants and antimony oxides (inorganic flame retardants) are the most important. It is an effective flame retardant and is widely used. In particular, a flame retardant using a combination of halogen and antimony is often used for flame retardancy of a curable resin in consideration of curing failure and the possibility of deterioration of physical properties after curing.

  However, a member using a resin composition to which a halogen flame retardant is added may burn unexpectedly despite being flame retardant. In addition, when the parts are incinerated, the problem of carcinogenicity caused by the generation of dioxins and the pollution of the atmosphere by these etc. against the regulation of environmentally hazardous substances such as RoHS / WEEE (Waste Electrical and Electronic Equipment) May cause. Antimony oxides are toxic and can cause antimony poisoning. Therefore, there is an increasing demand for non-halogenated and antimony-free resin compositions that are materials for members, particularly flame retardants that are additives.

  In addition, other inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide do not generate toxic gas when burning or incineration of components. Needs to be added in a large amount, which causes a problem of lowering mechanical properties such as breaking strength of members and formability.

  In addition, regarding phytate as disclosed in Patent Documents 1, 2, and 3, in addition to the above-mentioned problems of inorganic flame retardants, low solubility in resins or solvents, low liposolubility Problems such as whitening of the resulting resin and water resistance (hydrolysis property) of the material occur.

JP 2002-201475 A JP 2006-342333 A JP 2007-51212 A

  For this reason, the object of the present invention does not contain halogen, is highly soluble in a resin or a solvent, does not deteriorate the original characteristics of the resin such as mechanical properties and molding processability when the resin is added, does not cause whitening, An object of the present invention is to provide a flame retardant resin composition that satisfies UL standard (V-0) using a flame retardant that does not cause water resistance (hydrolysis).

 As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.

  That is, the present invention relates to a flame retardant resin composition comprising a resin and a flame retardant represented by the following general formula [1].

General formula [1]

(Wherein X ¹ and X ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group) In addition, X ¹ and X ² bonded to the same phosphate group may combine to form a new ring.)

  The flame retardant used in the present invention can be non-halogenated and antimony-free, and does not cause pollution. Further, even when added to a curable resin, the curability is not adversely affected, and a flame retarding effect can be exhibited with a relatively small amount. Further, by using a phytic acid ester such as the above general formula [1] instead of the phytate described in Patent Documents 1, 2, and 3, the solubility in a resin composition and a solvent is improved, and whitening in the resin is performed. (Crystallization) prevention and water resistance (non-hydrolyzable) are possible. By using this flame retardant, it is possible to provide a flame retardant resin composition that does not affect the original properties of the resin such as mechanical properties and molding processability when the resin is added.

  Hereinafter, the present invention will be described in detail.

  First, the flame retardant of the present invention will be described. The flame retardant of the present invention has a structure represented by the general formula [1]. By including a phosphate ester site that is known to exhibit a flame retardant effect, non-halogen and antimony free can be achieved, and the flame retardant effect can be achieved with a small amount of addition. By using a phytate such as the above general formula [1] instead of the phytate described in Patent Documents 1, 2, and 3, the solubility in a resin composition and a solvent is improved, and whitening (crystallization in a resin) ) Prevention and water resistance (non-hydrolyzable).

In the present invention, X ¹ and X ² in the general formula [1] are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted Represents a heterocyclic group.

In X ¹ and X ² , the substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 40 carbon atoms, more preferably a substituted alkyl group having 1 to 20 carbon atoms, for example, methyl An unsubstituted linear group such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group or the like Besides branched alkyl group, ethoxyethyl group, ethoxymethyl group, methoxymethyl group, methoxyethyl group, 2-phenylisopropyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α -Methylphenylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group, 3-methyloxetane-3-ylmethyl Group, 3-ethyloxetane-3-ylmethyl group, 2-isocyanatoethyl group, 2-aziridinylethyl group, 2- (tert-butylcarbodiimide) ethyl group, 2- (cyclohexylcarbodiimide) ethyl group, maleimidomethyl group , Hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 9-hydroxynonyl group, 1-hydroxylethyl group and the like.

In X ¹ and X ² , the substituted or unsubstituted cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 4 to 8 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo A heptyl group, a cyclooctyl group, an adamantyl group, etc. are mentioned.

In X ¹ and X ² , the substituted or unsubstituted aryl group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 40 carbon atoms, more preferably 6 to 6 carbon atoms. A substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 18 such as phenyl group, 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4-methyl-1-naphthyl group, 4-tert-butyl Ru-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-anthryl group, spirofluorenyl group, 4-malemidylphenyl group, 2- A benzocyclobutenyl group etc. are mentioned.

In X ¹ and X ² , the substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group containing O, N, S as a hetero atom, or a condensed polycyclic heterocyclic group Is mentioned. The heterocyclic group is preferably a heterocyclic group having 4 to 40 carbon atoms, more preferably a heterocyclic group having 4 to 20 carbon atoms, such as a thienyl group, a furyl group, a pyridyl group, a pyridinyl group. , Pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group, indolinyl group, quinolyl group, quinoxalyl group, acridinyl group, pyrrolyl group, pyranyl group, thiopyranyl group, dioxanyl group, piperidinyl group, morpholinyl group, piperazinyl group, carbazolyl group, oxazolyl Group, oxadiazolyl group, benzoxazolyl group, thiazolyl group, thiadiazolyl group, benzothiazolyl group, triazolyl group, imidazolyl group, imidazolpyridyl group, benzoimidazolyl group, pranyl group, morpholyl group, piperidyl group, piperazinyl group, benzofuryl Group, 2-benzothienyl group, indolyl group, acridinyl group, and phenanthrolyl group.

X ¹ and X ² bonded to the same phosphate group may combine to form a new ring.

  Representative examples of the compound represented by the general formula [1] which is the flame retardant of the present invention are shown in the following Tables 1 and 2, but the present invention is not limited to these representative examples.

Table 1

Table 2

  The compound group represented by the general formula [1] can be obtained by a known method. For example, as shown in the following reaction formula 1, myo-inositol and a halogenated phosphate can be obtained as starting materials.

Reaction formula 1

  The compound obtained above is isolated and purified from the reaction mixture according to conventional isolation methods such as extraction, distillation, column purification, recrystallization, reprecipitation, washing, filtration and drying. .

  Next, the flame retardant resin composition that can be prepared using the flame retardant of the present invention will be described in detail.

  The flame retardant resin composition of the present invention is obtained by blending the above flame retardant with a resin. Here, examples of the resin include a thermoplastic resin and a light / thermosetting resin. However, in the present invention, the thermoplastic resin and the light / thermosetting resin may be either a thermoplastic resin or a thermoplastic resin. A case where it consists of a mixed system of light and thermosetting resin is also possible.

  As the thermoplastic resin used in the present invention, conventionally known ones can be widely used. For example, polyethylene, polypropylene, polyisoprene, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polybutadiene, styrene resin, high-impact polystyrene, acrylonitrile. -Styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber- Styrene resin (AAS resin), polymethyl (meth) acrylate, polycarbonate, modified polyphenylene ether (PPE), polyamide, polyphenyle Sulfide, polyimide, polyetheretherketone, polysulfone, polyarylate, polyacetal, polyetherketone, polyethernitrile, polythioethersulfone, polyethersulfone, polybenzimidazole, polycarbodiimide, polyamideimide, polyetherimide, norbornene resin, Examples thereof include liquid crystal polymers and composite plastics.

  Among these thermoplastic resins, polyester, ABS resin, polycarbonate, modified polyphenylene ether, polyamide and the like can be preferably used.

  Conventionally known photo / thermosetting resins can be widely used, and examples thereof include polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicon resin, epoxy resin and the like.

  Among these photo / thermosetting resins, polyurethane, phenol resin, melamine resin, epoxy resin and the like can be particularly preferably used.

  In this invention, resin may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  The blending ratio of the flame retardant to these resins is not particularly limited, but is usually 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight per 100 parts by weight of the resin. Good part.

  The flame retardant resin composition of the present invention is a resin composition that exhibits an excellent flame retardant effect without using a halogen-containing compound such as chlorine and bromine as a flame retardant component, but is usually used. Known additives for flame retardancy can be added in appropriate combination as long as the excellent effects are not impaired.

  The additive for flame retardant is not particularly limited as long as it exhibits a flame retardant effect, and metal oxides such as zinc oxide, tin oxide, iron oxide, molybdenum oxide, copper oxide, manganese dioxide, etc. , Aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide treated with oxalic acid, magnesium hydroxide treated with nickel compound, etc., sodium carbonate, calcium carbonate, barium carbonate, sodium alkyl sulfonate, etc. Organochlorine compounds such as alkali metal salts or alkaline earth metal salts, chlorinated paraffin, perchlorocyclopentadecane, tetrabromobisphenol-A, epoxy resin, bis (tribromophenoxy) ethane, bis (tetrabromophthalimino) ethane Or organic bromine compound, antimony trioxide, tetraoxide Antimony compounds such as antimony, antimony pentoxide, sodium antimonate, red phosphorus, halogen-containing phosphate ester compounds, halogen-containing condensed phosphate ester compounds or phosphonate ester compounds, melamine, melamine cyanurate, melamine phosphate, melam, melem, Melon, succinoguanamine, guanidine sulfamate, ammonium sulfate, ammonium phosphate, ammonium polyphosphate, nitrogen amines such as alkylamine phosphate, boron compounds such as zinc borate, barium metaborate, ammonium borate, silicone polymers, silica, etc. Examples thereof include silicon compounds, thermally expandable graphite, and the like.

  These flame retardant additives can be used alone or in combination of two or more.

  Furthermore, conventionally well-known various resin additives can be mix | blended with the flame-retardant resin composition of this invention suitably in the range which does not impair the outstanding characteristic. Examples of the resin additive include flame retardants other than the above, anti-drip agent (anti-dripping agent), ultraviolet absorber, light stabilizer, antioxidant, light-blocking agent, metal deactivator, quencher, initiator, Examples include sensitizers, curing agents, heat curing aids, heat stabilizers, lubricants, mold release agents, colorants, antistatic agents, anti-aging agents, plasticizers, impact strength improvers, compatibilizers, and the like. .

  The ultraviolet absorber absorbs light energy and moves into an intramolecular proton to form a keto type molecule (benzophenone, benzotriazole type) or cause cis-trans isomerization (cyanoacrylate type). As a result, the absorbed energy is released as thermal energy and rendered harmless. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), and the like. 2-hydroxybenzophenones, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy) -3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- 2- (2′-hydroxyphenyl) benzotriazoles such as hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-t-octyl-6-benzotriazolyl) phenol , Phenyl salicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4 -Benzoates such as hydroxybenzoate, substituted oxanilides such as 2-ethyl-2'-ethoxy oxanilide, 2-ethoxy-4'-dodecyl oxanilide, and ethyl-α-cyano-β, β-diphenyl acrylate , Methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate and the like Acrylate, and the like.

  A light stabilizer is a component for decomposing hydroperoxide generated by light energy to generate a stable NO radical, NOR or N-OH and stabilizing it. For example, a hindered amine light stabilizer An agent can be mentioned. Specific examples thereof include 2,2,6,6, -tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6. -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidylsebacate, bis (1,2,2,6,6-pentamethyl-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 (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-t-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-t-octylamino-s-triazine polycondensation And 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate.

  An antioxidant is a component for stabilizing peroxide radicals such as hydroperoxy radicals generated or decomposing peroxides such as hydroperoxides generated during thermoforming or exposure to light. Examples of the antioxidant include hindered phenol antioxidants and peroxide decomposers. The former acts as a radical chain inhibitor, and the latter acts to decompose the peroxide generated in the system into more stable alcohols to prevent autooxidation.

  Examples of the hindered phenol antioxidant include 2,6-di-tert-butyl-4-methylphenol, styrenated phenol, and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy. Phenyl) propionate 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6) -T-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene 3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propioni Roxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

  The initiator is not particularly limited as long as it is a known one, and for example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acyl phosphine oxide compound, an aminocarbonyl compound and the like can be used.

  Thermosetting aids are compounds that contribute directly or catalytically to the curing reaction during thermosetting. The thermosetting aid is appropriately selected depending on the thermosetting component used. Moreover, the curing conditions for the carboxyl group-containing photosensitive urethane resin and the thermosetting component can be appropriately selected depending on the thermosetting component and the thermosetting aid used.

  Specific examples of the thermosetting aid include tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, and / or the like. Salts thereof; 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl] -1] -ethyl-s-triazine and the like imidazoles and / or salts thereof; 1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5 -Diazabicyclo compounds such as nonene and 1,4-diabicyclo [2,2,2,] octane; tributyl Phosphines such as sphin, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine; tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenyl Phosphonium salts such as borates; and other compounds that contribute to the curing reaction both catalytically and directly include dicyandiamide and carboxylic acid hydrazide. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

  Examples of the peroxide decomposer include organophosphorus peroxide decomposers such as tris (nonylphenyl) phosphite, triphenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, and dilauryl- 3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl Examples thereof include organic sulfur peroxide decomposing agents such as −3,3′-thiodipropionate and 2-mercaptobenzimidazole.

The light shielding agent is a component for preventing light from reaching the polymer bulk. Specific examples thereof include rutile type titanium oxide (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), cerium oxide (CeO ₂ ), and the like.

  The metal deactivator is a component for inactivating heavy metal ions in the resin with a chelate compound. Specific examples thereof include benzotriazole and derivatives thereof (specifically, 1-hydroxybenzotriazole and the like).

  A quencher is a component for deactivating functional groups such as hydroperoxide and carbonyl group in a polymer by energy transfer, and specific examples thereof include organic nickel.

  Further, conventionally known various additives may be further blended for the purpose of imparting antifogging properties, antifungal properties, antibacterial properties, or other functionalities.

  The flame retardant resin composition of the present invention is obtained by weighing a predetermined amount or an appropriate amount of the flame retardant of the present invention and, if necessary, various additives for flame retardant and other additives, and adding them to the resin. It can be obtained by mixing and kneading by the above method. For example, a mixture of powder, beads, flakes or pellets of each component, a single screw extruder, an extruder such as a twin screw extruder, a Banbury mixer, a pressure kneader, a two roll, a three roll, etc. The flame retardant resin composition of the present invention can be obtained by kneading with the use of the above. Moreover, when it is necessary to mix | blend a liquid, it can knead | mix with said extruder or a kneader etc. using a well-known liquid injection | pouring apparatus.

  Moreover, molded bodies, such as a resin board, a sheet | seat, a film, are obtained by hardening the obtained resin composition with a heat | fever or light.

  When the resin composition is cured by heat or light, the flame retardant represented by the general formula [1] may be incorporated by reacting with the resin.

  The flame retardant resin composition of the present invention thus obtained can be used in a wide range of industrial fields such as packages, building materials, fibers, household goods, electrical / electronic products, OA equipment, office equipment, communication equipment, automobile-related members, and the like. Can be used.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

  Prior to the examples, the synthesis of the compound used as the flame retardant of the present invention and the synthesis of the urethane resin solution used in producing the flame retardant resin composition will be described.

Synthesis example 1
Method for synthesizing compound 1

  Myo-inositol (10.00 g), triethylamine (39 g) and toluene (100 mL) were placed in a 500 ml flask and cooled to 5 ° C. under a nitrogen atmosphere. Halogenated phosphoric acid ester 1 (48 g) dissolved in toluene (100 ml) was added dropwise over 1 hour. After completion of the addition, the mixture was refluxed and stirred for 2 hours. The reaction solution was allowed to cool, 200 ml of distilled water was added, and the mixture was separated to obtain an organic layer. The aqueous layer was washed 3 times with 50 ml of chloroform, and the obtained organic layer was added to the previous organic layer. The organic layer was dried over magnesium sulfate, filtered and solvent removed. Compound 1 was obtained. (19.8 g) was obtained. TOF-MS (autoflex II manufactured by BRUKER DALTONICS) m / z = 828 (molecular weight: 828).

Halogenated phosphate ester 1

Synthesis Examples 2-50
In the synthesis example 1 described above, the compounds shown in Table 3 were synthesized by changing the halogenated phosphate used to a halogenated phosphate corresponding to each compound.

  About the structure of the compound which is the flame retardant of this invention obtained by the synthesis examples 1-50, it identified by the TOF-MS spectrum. Table 3 shows the synthesized compounds, the halogenated phosphates used, and the measurement results of the mass spectra of the compounds. The compound numbers are the same as those described in Tables 1 and 2 in this specification.

Table 3

Synthesis Example 51
To a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, PTG850 sn (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, weight average molecular weight = about 850, hydroxyl value = 129 mgKOH / g) ) 55 parts, dimethylol butanoic acid (Nippon Kasei Co., Ltd.) 178 parts, and 375 parts of cyclohexanone as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and uniformly dissolved. Subsequently, 267 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 10,000, a molecular weight distribution of 2.03, and an actually measured acid value of resin solids of 138 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 85 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. A small amount of sampling was performed after cooling, and cyclohexanone was further added to adjust the solid content to 50.0% to obtain a urethane resin (A-1) solution. The ethylenically unsaturated group equivalent of the resin solid content by this design was 1156 g / eq, the weight average molecular weight in terms of polystyrene was 12800, the molecular weight distribution was 2.25, and the acid value of the resin solid content by actual measurement was 68 mgKOH / g. .

Example 1
10 parts of Compound 1 is added to a resin composed of 75 parts of an aromatic polycarbonate resin (1783100-0050 manufactured by ACROS) and 25 parts of ABS resin (430137-250G manufactured by Aldrich), mixed with a mixer, and then used with a lab plast mill. And kneaded to obtain a flame retardant resin composition. A sample A having a thickness of 2 mm was produced from the composition by a hot press, and the following evaluation was performed. The results are shown in Table 4.

Flame Retardancy Evaluation Sample A was tested according to the UL94 flame retardant test and evaluated according to the following criteria.
V-0 ◎ ... Flame-out time after ignition is within 5 seconds.
V-0 ○: Flame extinguishing time after ignition is within 5 to 10 seconds.
V-1 .... Flame extinguishing time after ignition is within 10 to 30 seconds.
The high flame retardance is in the order of V-0 ◎> V-0 ○> V-1.

Crystallization Evaluation The surface layer of Sample A which was allowed to stand at 40 ° C. for one week was observed with a microscope and evaluated according to the following criteria.
◯: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

Examples 2-50
The compound 1 of Example 1 was changed into the compound shown in Table 4, and the same operation was performed. The results are shown in Table 4.

Comparative Example 1
A similar experiment was conducted by changing Compound 1 of Example 1 to sodium phytate which is a known compound. The results are shown in Table 4.

Table 4

  As is apparent from Table 4, the flame retardant resin of the present invention showed high flame retardancy without whitening.

Examples 51-59
10 parts of compound 2 was added to 100 parts of each resin shown in Table 5, mixed with a mixer, and then melt-kneaded using a lab plast mill to obtain a flame-retardant resin composition. A sample B having a thickness of 2 mm was produced from the composition by a hot press, and the following evaluation was performed. The results are shown in Table 5.

Flame retardancy evaluation Sample B was tested according to the UL94 flame retardancy test and evaluated according to the following criteria.
V-0 ◎ ... Flame-out time after ignition is within 5 seconds.
V-0 ○: Flame extinguishing time after ignition is within 5 to 10 seconds.
V-1 .... Flame extinguishing time after ignition is within 10 to 30 seconds.
The high flame retardance is in the order of V-0 ◎> V-0 ○> V-1.

Crystallization Evaluation Sample B was allowed to stand at 40 ° C. for one week, and the surface layer was observed with a microscope and evaluated according to the following criteria.
◯: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

Table 5

  As is apparent from Table 5, in various resins, the flame retardant resin of the present invention showed high flame retardancy without whitening.

Example 60
100 parts of the urethane resin (A-1) solution obtained in Synthesis Example 51, 15 parts of HP7200 (manufactured by Dainippon Ink Chemical Co., Ltd .: dicyclopentadiene type epoxy) as the thermosetting component, and DICY7 (Ajinomoto Fine Co., Ltd.) as the thermosetting aid (Techno Co., Ltd .: Dicyandiamide) 0.5 part, 15 parts of compound 4 as a flame retardant were blended and kneaded with 3 rolls to prepare the flame retardant resin composition of the present invention. The obtained flame retardant resin composition was applied on a 25 μm-thick polyimide film so that the dry film thickness was 20 μm, dried for 30 minutes in a hot air dryer at 80 ° C., and then at 120 ° C. for 1 hour, 150 Sample C was obtained by thermosetting at 2 ° C. for 2 hours. This sample C was evaluated as follows. The results are shown in Table 6.

Flame retardancy evaluation Sample C was tested according to the UL94 flame retardancy test and evaluated according to the following criteria.
VTM-0 ◎ ... UL V-0 equivalent and extinguishing time after ignition is within 3 seconds.
VTM-0 ○ ... UL V-0 equivalent, extinguishing time after ignition within 3-6 seconds.
HB ◎ ... Extinguish from UL HB to 25mm from ignition point.
HB ○ ... Extinguishes flames from the ignition point to 25-100mm, equivalent to UL HB.
X: Not extinguished by 100 mm in UL HB test or complete combustion.
The high flame retardancy is in the order of VTM-0-> VTM-0 ○> HB ◎> HB ○> ×.

Crystallization Evaluation Sample C was allowed to stand at 40 ° C. for one week, and the surface layer was observed with a microscope and evaluated according to the following criteria.
◯: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

Examples 61-109
Compound 1 of Example 60 was changed to the compounds shown in Table 6, and the same operation was performed. The results are shown in Table 6.

Comparative Example 2
A similar experiment was conducted by changing Compound 1 of Example 60 to sodium phytate which is a known compound. The results are shown in Table 6.

Table 6

  As is apparent from Table 6, the flame retardant resin of the present invention showed high flame retardancy without whitening.

Example 110
100 parts of the urethane resin (A-1) solution obtained in Synthesis Example 51, Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd .: 2-methyl-1- [4- (methylthio) phenyl] as a photopolymerization initiator -2-morpholino-1-propane) 1.0 part, DETX-S (Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone) 0.5 part, Aronics M-310 as an ethylenically unsaturated group-containing compound (Toagosei Co., Ltd .: trimethylolpropane PO-modified triacrylate) 3.0 parts, HP7200 as a thermosetting component (Dainippon Ink Chemical Co., Ltd .: dicyclopentadiene type epoxy) 25.0 parts, as thermosetting aid DICY7 (Ajinomoto Fine Techno Co., Ltd .: Dicyandiamide) 0.5 parts, BARIFINE B as additive F-10 (Sakai Chemical Industry Co., Ltd .: Barium sulfate) 15.0 parts, Blue paste (blue pigment / base resin (phenol resin) / solvent (carbitol acetate) = 28/12/60) 0.5 parts, book As the flame retardant of the invention, 80.0 parts of Compound 1 was blended and kneaded with three rolls to prepare the flame retardant resin composition of the present invention. The obtained flame retardant resin composition was applied onto Kapton 100H (manufactured by Toray DuPont Co., Ltd .: polyimide film (25 μm thickness)) so that the dry film thickness was 25 μm, and 30 ° C. with a hot air dryer at 80 ° C. After being partially dried, it was cooled to room temperature. Next, using an ultraviolet exposure device (USHIO INC .: “UVC-2534 / 1MNLC3-AA08”, 120 W / cm metal halide lamp, 1 lamp), ultraviolet light with an integrated light quantity of 300 mJ / cm ² was irradiated and hot air at 150 ° C. It was heat-cured (post-cured) for 1 hour with a dryer. The obtained cured product was cooled to room temperature. This was designated as sample D. The sample D was evaluated as follows. The results are shown in Table 7.

Flame retardancy evaluation Sample D was tested according to the UL94 flame retardancy test and evaluated according to the following criteria.
VTM-0 ◎ ... UL V-0 equivalent and extinguishing time after ignition is within 3 seconds.
VTM-0 ○ ... UL V-0 equivalent, extinguishing time after ignition within 3-6 seconds.
HB ◎ ... Extinguish from UL HB to 25mm from ignition point.
HB ○ ... Extinguishes flames from the ignition point to 25-100mm, equivalent to UL HB.
X: Not extinguished by 100 mm in UL HB test or complete combustion.
The high flame retardancy is in the order of VTM-0-> VTM-0 ○> HB ◎> HB ○> ×.

Crystallization Evaluation The sample D was allowed to stand at 40 ° C. for one week, and the surface layer was observed with a microscope and evaluated according to the following criteria.
◯: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

Examples 111-159
Compound 1 of Example 110 was changed to the compounds shown in Table 7, and the same operation was performed. The results are shown in Table 7.

Comparative Example 3
A similar experiment was conducted by changing Compound 1 of Example 110 to sodium phytate which is a known compound. The results are shown in Table 7.

Table 7

  As is apparent from Table 7, the flame retardant resin of the present invention showed high flame retardancy without whitening.

  From the above results, it is shown that the flame retardant resin composition using the flame retardant of the present invention does not whiten (crystallize) and has high flame resistance satisfying UL standard (V-0). It was. From the above, it can be suitably used in applications such as packages, building materials, textiles, daily goods, electrical / electronic products, OA equipment, office equipment, communication equipment, and automobile-related members.

Claims (1)

A flame retardant resin composition comprising a resin and a flame retardant represented by the following general formula [1].
General formula [1]

(Wherein X ¹ and X ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group) In addition, X ¹ and X ² bonded to the same phosphate group may combine to form a new ring.)