JP2004115815A - Flame-retardant, flame-retardant resin composition, and flame-retardant resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant having the advantages that it contains no halogen, has a high melting point, has low volatility, does not lower characteristics proper to a resin, and so forth. <P>SOLUTION: This flame-retardant comprises at least one phosphazene compound selected from a group consisting of cyclic phosphazene compounds represented by formula (1) (wherein m denotes an integer of 3-25; and Ph denotes a phenyl group) and straight chain phosphazene compounds represented by formula (2) (wherein X denotes a -N=P(OPh)<SB>3</SB>group or a -N=P(O)OPh group; Y denotes a -P(OPh)<SB>4</SB>group or a -P(O)(OPh)<SB>2</SB>group; n denotes an integer of 3-1,000; and Ph is as defined above). <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a flame retardant, a flame-retardant resin composition, and a flame-retardant resin molded article.

Plastics are used for electrical and electronic products, office automation equipment, office equipment, communication equipment, etc. due to their excellent moldability, mechanical properties, and appearance. In these applications, it is necessary to make the resin flame-retardant due to problems such as heat generation and ignition of internal components.

In order to impart flame retardancy to a thermoplastic resin or a thermosetting resin, it is common to add a flame retardant before molding the resin. As the flame retardant, inorganic hydroxides, organic phosphorus compounds, organic halogen compounds, halogen-containing organic phosphorus compounds and the like are known.

中 で Among these, the flame retardants having excellent flame retardant effects are halogen-containing compounds such as organic halogen compounds and halogen-containing organic phosphorus compounds.

However, these halogen-containing compounds are thermally decomposed at the time of resin molding to generate hydrogen halide, and cause corrosion of a mold, deterioration and coloring of the resin. Further, when the resin is burned due to a fire or the like, there is a problem that harmful gas or smoke is generated for living things such as hydrogen halide.

On the other hand, flame retardants that do not contain halogen are inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide and organic phosphorus compounds.

However, inorganic hydroxides exhibit flame retardancy due to water generated by thermal decomposition, and therefore have a low flame retardant effect. Therefore, a large amount of inorganic hydroxide must be added. There is a disadvantage that.

Organic phosphorus compounds are widely used because of their relatively good flame-retardant effects, and triphenyl phosphate (TPP), tricresyl phosphate (TCP) and the like are known as typical ones. I have. However, since these organic phosphorus compounds are liquids or low-melting-point solids, they have high volatility and have problems such as lowering the molding temperature of the resin, blocking and bleeding (juicing) during kneading.

Furthermore, the resin compositions containing these organic phosphorus compounds have a drawback that dripping (drip of molten resin) and fire spread due to the dripping occur during combustion. Therefore, an organic phosphorus compound is added to a resin, and a flame retardancy test UL-94 (Testing for Flammability of Plastic Material S for Parts in Devices & Appliances) is used as a standard for evaluating flame retardancy. In order to achieve “Evaluation V-0 (combustion does not continue for a certain period of time, ignite cotton, and there is no molten dripping)”, for example, polytetrafluoroethylene is used as an agent for preventing molten resin from dripping during combustion. It is necessary to add a fluorinated resin such as fluorinated ethylene resin (PTFE). However, as described above, these fluororesins contain a halogen element and generate toxic gases to the human body when burned.

Therefore, it does not contain halogen, has a high melting point, low volatility, and does not degrade the original properties of the resin such as mechanical properties and moldability, and has no problems such as blocking or bleeding during kneading, and during combustion. Development of a new flame retardant that does not cause dripping has been desired.

The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, has found that a specific partially crosslinked phenoxyphosphazene compound can be a desired flame retardant. The present invention has been completed based on such findings.

According to the present invention, the general formula (1)

[Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ]
A cyclic phosphazene compound represented by the general formula (2):

[Where X represents a group -N = P (OPh) ₃ or -N = P (O) OPh, and Y represents a group -P (OPh) ₄ or a group -P (O) (OPh) ₂ . n shows the integer of 3-1000. Ph is the same as above. ]
At least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula: is an o-, m-, p-phenylene group, a biphenylene group and a group

Wherein A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—. ]
A compound cross-linked by at least one type of cross-linking group selected from the group consisting of: wherein the cross-linking group is interposed between two oxygen atoms from which the phenyl group of the phosphazene compound has been eliminated; The crosslinked phenoxyphosphazene compound is characterized in that the content ratio of the phenyl group in the compound is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2). A flame retardant (hereinafter, this flame retardant is referred to as “flame retardant A”) is provided.

The flame retardant A comprising the crosslinked phenoxyphosphazene compound of the present invention does not contain a halogen, and therefore thermally decomposes at the time of resin molding to generate hydrogen halide, without causing mold corrosion, resin deterioration and coloring. Also, when the resin burns due to a fire or the like, it does not generate harmful gases or smoke for living things such as hydrogen halide. The crosslinked phenoxyphosphazene compound of the present invention has low volatility, does not lower the molding temperature of the resin, and causes problems such as blocking and bleeding (juicing) during kneading and dripping during combustion. There is no. Furthermore, the blending of the flame retardant A does not lower the mechanical characteristics such as impact resistance, heat resistance, and the inherent characteristics of the resin such as moldability.

Further, according to the present invention, (a) a flame-retardant resin composition comprising 0.1 to 100 parts by weight of a flame retardant A per 100 parts by weight of a thermoplastic resin or a thermosetting resin; A flame-retardant resin composition in which 0.1 to 100 parts by weight of a flame retardant A and 0.01 to 50 parts by weight of an inorganic filler are blended with respect to 100 parts by weight of a resin or a thermosetting resin; Flame retardant resin composition containing 0.1 to 50 parts by weight of flame retardant A and 0.1 to 50 parts by weight of halogen-free organic phosphorus compound per 100 parts by weight of curable resin, and (d) thermoplastic resin A flame-retardant resin composition is provided in which 0.1 to 100 parts by weight of a flame retardant A and 0.01 to 2.5 parts by weight of a fluororesin are blended with respect to 100 parts by weight.

According to the present invention, there is also provided a flame-retardant resin molded article obtainable by molding the flame-retardant resin composition of the above (a) to (d).

Further, at least one phosphazene compound selected from the group consisting of the cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2) is used as an inorganic filler or halogen. It has been found that the desired effect of the present invention as described above is exhibited also when used in combination with an organic phosphorus compound containing no.

According to the present invention, a flame retardant comprising at least one phosphazene compound selected from the group consisting of a cyclic phosphazene compound represented by the general formula (1) and a linear phosphazene compound represented by the general formula (2) (Hereinafter, this flame retardant is referred to as “flame retardant B”).

Further, according to the present invention, (e) a flame retardant obtained by blending 0.1 to 100 parts by weight of a flame retardant B and 0.01 to 50 parts by weight of an inorganic filler with respect to 100 parts by weight of a thermoplastic resin or a thermosetting resin. 0.1 to 50 parts by weight of a flame retardant B and 0.1 to 50 parts by weight of a halogen-free organic phosphorus compound were added to 100 parts by weight of the thermoplastic resin composition or (f) the thermoplastic resin or the thermosetting resin. A flame retardant resin composition is provided.

According to the present invention, there is also provided a flame-retardant resin molded article obtainable by molding the flame-retardant resin composition of the above (e) to (f).

Further, when at least one phosphazene compound selected from the group consisting of a cyclic phosphazene compound represented by the following general formula (3) and a linear phosphazene compound represented by the general formula (4) is used as a flame retardant: Also found that the desired effects of the present invention as described above were exhibited.

According to the present invention, general formula (3)

Wherein m is the same as above. R ¹ represents a cyano-substituted phenyl group. R ² is an alkyl group having 1 to 18 carbon atoms,

Or group

Is shown. Here, R ³ represents a hydrogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an allyl group or a phenyl group. If the R ² there are two or more, R ² may be the same or different. p and q are p> 0 and q ≧ 0, and are real numbers satisfying p + q = 2. ]
A cyclic phosphazene compound represented by the general formula (4):

Wherein n, R ¹ , R ² , p and q are the same as above. X ′ is a group —P (OR ¹ ) ₄ , a group —P (OR ¹ ) ₃ (OR ² ), a group —P (OR ¹ ) ₂ (OR ² ) ₂ , and a group —P (OR ¹ ) (OR ² ). _3, group -P (oR ²⁾ _4, a group ^{-P (O) (oR 1)} 2, group ^{-P (O) (oR 1)} (oR 2) or a group ^{-P (O) (oR 2)} 2 Y ′ is a group -N = P (OR ¹ ) ₃ , a group -N = P (OR ¹ ) ₂ (OR ² ), a group -N = P (OR ¹ ) (OR ² ) ₂ , a group -N = P (OR ² ) ₃ , a group —N ＝ P (O) OR ¹ or a group —N ＝ P (O) OR ² . ]
And a flame retardant comprising at least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula (hereinafter, this flame retardant is referred to as "flame retardant C").

According to the present invention, there is provided a flame-retardant resin composition in which 0.1 to 100 parts by weight of a flame retardant C is blended with 100 parts by weight of a thermoplastic resin or a thermosetting resin.

According to the present invention, there is also provided a flame-retardant resin molded article obtainable by molding the above-described flame-retardant resin composition.

Flame retardant (a) Flame retardant A
First, the flame retardant A will be described.

The crosslinked phenoxyphosphazene compound of the present invention is obtained by reacting a dichlorophosphazene oligomer (a mixture of a cyclic dichlorophosphazene oligomer and a linear dichlorophosphazene oligomer) with a phenol alkali metal salt and an aromatic dihydroxy compound alkali metal salt. It can be manufactured by doing. As the dichlorophosphazene oligomer, a cyclic dichlorophosphazene oligomer and a linear dichlorophosphazene oligomer may be separated and used alone. The alkali metal salt of phenol and the alkali metal salt of the aromatic dihydroxy compound may be mixed and used for the reaction, or the alkali metal salt of the phenol may be reacted and further reacted with the alkali metal salt of the aromatic dihydroxy compound. Or vice versa.

The dichlorophosphazene oligomer can be produced according to a known method such as JP-A-57-87427, JP-B-58-19604, JP-B-61-1363, and JP-B-62-20124. As an example, first, ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride, and chlorine) may be reacted with chlorobenzene as a solvent at about 120 to 130 ° C. for dehydrochlorination.

ア ル カ リ Examples of the alkali metal salt of phenol include a phenol Na salt, a K salt, and a Li salt. As the alkali metal salt of the aromatic dihydroxy compound, any alkali metal salt of a known compound having one or two or more benzene rings in the molecule and having two hydroxy groups can be used. For example, resorcinol , Hydroquinone, catechol, 4,4'-isopropylidene diphenol (bisphenol-A), 4,4'-sulfonyl diphenol (bisphenol-S), 4,4'-thiodiphenol, 4,4'-oxydi Examples thereof include alkali metal salts such as phenol and 4,4'-diphenol. The alkali metal salt is not particularly limited, but a Li salt is preferred. As the alkali metal salt of the aromatic dihydroxy compound, one kind can be used alone, or two or more kinds can be used in combination.

The amount of the alkali metal salt of the phenol and the alkali metal salt of the aromatic dihydroxy compound to be used for the dichlorphosphazene oligomer is usually about 1 to 1.5 equivalents (the chlorine amount of the dichlorophosphazene oligomer is a total amount of both alkali metal salts). (Based on the amount of chlorine), preferably about 1 to 1.2 equivalents (based on the amount of chlorine). The use ratio of the two alkali metal salts (alkali metal salt of aromatic dihydroxy compound / alkali metal salt of phenol, molar ratio) is not particularly limited and can be appropriately selected from a wide range, but is usually about 1/2000 to 1/4. And it is sufficient. Within this range, the desired crosslinked phenoxyphosphazene compound of the present invention can be obtained.

If this usage ratio is significantly smaller than 1/2000, the effect of the cross-linking compound will be reduced, and it may be difficult to solve the above-mentioned problems such as prevention of melting and dropping. On the other hand, when the use ratio is much larger than 1/4, the crosslinking proceeds excessively, and the obtained crosslinked phenoxyphosphazene compound becomes insoluble and infusible, and there is a possibility that the dispersibility in the resin may be reduced.

The reaction between the dichlorophosphazene oligomer and both alkali metal salts is usually carried out at a temperature of about room temperature to about 150 ° C. in a solvent such as aromatic hydrocarbons such as toluene and halogenated aromatic hydrocarbons such as chlorobenzene. Done.

The terminal groups X and Y in the general formula (2) vary depending on the reaction conditions and the like. When a mild reaction is performed under normal reaction conditions, for example, in a non-aqueous system, X becomes -N = P (OPh ₃ ) The reaction was carried out under reaction conditions in which Y had a structure of -P (OPh) ₄ and water or an alkali metal hydroxide was present in the reaction system, or under severe reaction conditions in which a transfer reaction occurred. In this case, in addition to the structure in which X is -N = P (OPh) ₃ and Y is -P (OPh) ₄ , X is -N = P (O) OPh, and Y is -P (O) (OPh). The structure of the structure ₂ is mixed.

Thus, the crosslinked phenoxyphosphazene compound of the present invention is produced. The decomposition temperature of the crosslinked phenoxyphosphazene compounds of the present invention is generally in the range of 250-350C.

In the above method, when the dichlorophosphazene oligomer is reacted with only an alkali metal salt of phenol without using an alkali metal salt of an aromatic dihydroxy compound, the cyclic phosphazene compound represented by the general formula (1) A linear phosphazene compound represented by the general formula (2) is produced. However, when an alkali metal salt of an aromatic dihydroxy compound is used together with an alkali metal salt of phenol, the cyclic phosphazene compound represented by the general formula (1) or the linear phosphazene compound represented by the general formula (2) can be used. The phenoxyphosphazene compound of the present invention in which a part of the phenyl group is replaced by a crosslinking group is produced.

The content ratio of the phenyl group in the crosslinked phenoxyphosphazene compound of the present invention is 50 to 99.9%, preferably 70, based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2). ~ 90%.

The crosslinked phenoxyphosphazene compound of the present invention obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration, and drying.

(b) Flame retardant B
Next, the flame retardant B will be described.

環状 The cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2) are both known compounds. These phosphazene compounds are described, for example, in James E. Mark, Harry R. Allcock, Robert West, "Inorganic Polymers" Pretice-Hall International, Inc., 1992, p61-p140.

The cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2) can be prepared, for example, by converting an alkali metal salt of an aromatic dihydroxy compound into the above-mentioned crosslinked phenoxyphosphazene compound. Except not using it, it is manufactured by the same method as above.

The phosphazene compound obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration and drying.

Specific examples of the cyclic phosphazene compound represented by the general formula (1) include, for example, hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at 120 to 130 ° C. A phosphazene compound in which a phenoxy group is substituted for a chlorophosphazene mixture in which cyclic and linear n is represented by an integer of 3 to 25, and hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlor from the chlorophosphazene mixture. A single substance such as cyclopentaphosphazene is taken out and a cyclic phosphine such as hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene or decafenoxycyclopentaphosphazene in which these single substances are substituted with a phenoxy group is used. Emission compounds. Further, when the linear phosphazene compound represented by the general formula (2) is specifically exemplified, for example, hexachlorocyclotriphosphazene is heated to 220 to 250 ° C., and n obtained by ring-opening polymerization is 3 to 1000. And a linear phosphazene compound in which dichlorophosphazene represented by the following formula is substituted by a phenoxy group.

Among these, a phosphazene compound in which a phenoxy group is substituted for a chlorphosphazene mixture in which cyclic and linear n is represented by an integer of 3 to 25 is preferable.

(c) Flame retardant C
Next, the flame retardant C will be described.

As the phosphazene compound represented by the general formula (3), for example, R ¹ is a cyano-substituted phenyl group, R ² is an alkyl group having 1 to 8 carbon atoms,

Or group

And a cyclic phosphazene compound in which R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7, and q is 0.3 to 0.7.

As the phosphazene compound represented by the general formula (4), for example, R ¹ is a cyano-substituted phenyl group, R ² is an alkyl group having 1 to 8 carbon atoms,

Or group

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7, and q is 0.3 to 0.7. preferable.

Examples of the cyano-substituted phenyl represented by R ¹ include 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl and the like.

More specifically, as the phosphazene compound represented by the general formula (3) or (4), for example, a cyclic phosphazene such as cyclotriphosphazene, cyclotetraphosphazene, cyclopentaphosphazene, etc., in which a cyanophenoxy group and a phenoxy group are mixed and substituted. And a linear phosphazene compound.

Specific examples of the cyclic phosphazene compound in which a cyanophenoxy group and a phenoxy group are mixed and substituted include, for example, monocyanophenoxypentaphenoxycyclotriphosphazene, dicyanofenoxytetraphenoxycyclotriphosphazene, tricyanophenoxytriphenoxycyclotriphosphazene, and tetracyanophenoxy. Cyclotriphosphazene compounds such as diphenoxycyclotriphosphazene and pentacyanophenoxymonophenoxycyclotriphosphazene, monocyanophenoxypeptaphenoxycyclotetraphosphazene, dicyanphenoxyhexaphenoxycyclotetraphosphazene, tricyanophenoxypentaphenoxycyclotetraphosphazene, tetra Cyanophenoxytetraphenoxycyclotetrafos Cyclotetraphosphazenes such as azazen, pentacyanophenoxytriphenoxycyclotetraphosphazene, hexacyanophenoxydiphenoxycyclotetraphosphazene, and heptacyanophenoxymonophenoxycyclotetraphosphazene; and cyclopentaphosphazene compounds in which cyanophenoxy and phenoxy groups are mixed and substituted. And other cyclic phosphazene compounds.

直 鎖 Further, examples of the linear phosphazene compound include a linear phosphazene compound in which a cyanophenoxy group and a phenoxy group are mixed and substituted.

These phosphazene compounds may be used alone or as a mixture of two or more.

中 で も Among the phosphazene compounds, phosphazene oligomers (mixtures of cyclic and linear products) in which a cyanophenoxy group and a phenoxy group are mixed and substituted are preferable from the viewpoint of the production method, availability, and the like. A phosphazene oligomer having a content ratio of cyanophenoxy group to phenoxy group of 1: 7 to 7: 1 is particularly preferable.

The phosphazene compound having a cyanophenoxy group (phosphazene compound represented by the general formula (3) or (4)) of the present invention is produced by various methods.

As a raw material for producing a phosphazene compound having a cyanophenoxy group, for example, as shown in the following reaction formula-1, hexachlorocyclotriphosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at 120 to 130 ° C. Cyclic and linear phosphazene compounds such as chlorocyclotetraphosphazene can be used. In this reaction, a solvent such as tetrachloroethane or chlorobenzene can be used as a solvent.
Reaction formula-1

In addition, as the production raw material, hexachlorocyclotriphosphazene is taken out from the cyclic and linear mixture obtained by the method shown in the above reaction formula-1, and is heated to 220 to 250 ° C. to obtain ring-opening polymerization. Dichlorophosphazene can be used as a linear phosphazene compound (see the following reaction formula-2).
Reaction formula-2

The method for producing the phosphazene compound having a cyanophenoxy group of the present invention includes, for example, the cyclic or linear phosphazene compound obtained above, an alkali metal salt of cyanophenol mixed with a desired ratio, and phenol (on an aromatic ring). C1 to C10 alkyl group, allyl group, and phenol substituted with phenyl group, and naphthol (naphthol having C1 to C10 alkyl group, allyl group and phenyl group substituted on aromatic ring) And a mixture with at least one alkali metal salt selected from the group consisting of alcohols having 1 to 18 carbon atoms (hereinafter referred to as "phenols").

For example, a dehydration reaction is performed from a mixture of cyanophenol and phenols mixed in a desired ratio with sodium hydroxide to prepare a sodium salt of cyanophenol and a sodium salt of phenols. In this dehydration reaction, water may be simply removed, and a solvent may or may not be used. When a solvent is used, benzene, toluene, xylene, chlorobenzene, and the like are selected, and azeotropic distillation with the solvent may increase the dehydration efficiency. Next, after adding the cyclic or linear phosphazene compound obtained above to the sodium salt of cyanophenol and the sodium salt of phenols, the mixture is heated at 50 to 150 ° C. for 1 to 24 hours to perform a substitution reaction, A desired phosphazene compound having a cyanophenoxy group can be obtained.
Reaction formula-3

The desired phosphazene compound having a cyanophenoxy group can be produced from the dehydration reaction and the substitution reaction as described above. Considering the efficiency of each operation, chlorobenzene is selected as the solvent. When chlorobenzene is used as a solvent, the substitution reaction is completed when the chlorbenzene is refluxed for about 12 hours.

Further, as a production method other than the above, a method of reacting an alkali metal salt of cyanophenol and an alkali metal salt of phenol with a separated or purified cyclic or linear dichlorophosphazene, or a method of producing cyanophenol with a dichlorophosphazene oligomer A method in which an alkali metal is reacted and then an alkali metal salt of a phenol is sequentially reacted is exemplified.

The phosphazene compound having a cyanophenoxy group obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration and drying.

Flame retardant resin composition The flame retardant resin composition of the present invention is obtained by blending the above flame retardant A, B or C with a thermoplastic resin or a thermosetting resin. Hereinafter, unless otherwise specified, the flame-retardant resin composition of the present invention is a general term for a resin composition having any one of a thermoplastic resin and a thermosetting resin as a matrix.

(a) Thermoplastic resin As the thermoplastic resin used in the present invention, conventionally known thermoplastic resins can be widely used, for example, polyethylene, polypropylene, polyisoprene, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polybutadiene, styrene resin, Impact-resistant 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 , Polyphenylene sulfide, polyimide, polyetheretherketone, polysulfone, polyarylate, polyetherketone, polyethernitrile, polythioethersulfone, polyethersulfone, polybenzimidazole, polycarbodiimide, polyamideimide, polyetherimide, liquid crystal polymer, composite Plastics and the like.

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

に お い て In the present invention, the thermoplastic resins are used alone or as a mixture of two or more.

(b) Thermosetting resin As the thermosetting resin, conventionally known ones can be widely used, and polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, epoxy resin and the like can be used. Can be mentioned.

ポ リ ウ レ タ ン Among these thermosetting resins, polyurethane, phenol resin, melamine resin, epoxy resin and the like can be particularly preferably used.

The epoxy resin is not particularly limited, and a conventionally known epoxy resin can be widely used. Examples thereof include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, and glycidylamine. Examples include a series epoxy resin, a heterocyclic epoxy resin, a urethane-modified epoxy resin, and a brominated bisphenol-A type epoxy resin.

に お い て In the present invention, the thermosetting resin is used singly or as a mixture of two or more.

The blending ratio of the flame retardant A, the flame retardant B or the flame retardant C with respect to the thermoplastic resin or the thermosetting resin is not particularly limited, but is usually per 100 parts by weight of the thermoplastic resin or the thermosetting resin. 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight.

(c) Inorganic filler An inorganic filler can be added to the flame-retardant resin composition of the present invention in order to further improve the anti-dripping property.

Conventionally, these inorganic fillers have been mainly used as reinforcing materials for improving the mechanical properties of resins. However, the present inventor, by coexisting the above-mentioned flame retardant and the inorganic filler in the resin, they act synergistically, not only the improvement of mechanical properties, but also the flame retardant effect of the above-mentioned flame retardant, especially It has been found that the anti-dripping effect is significantly improved.

When the flame retardant and the inorganic filler coexist in the resin, the resin surface layer becomes dense and strong, suppresses diffusion of generated gas on the resin surface during combustion, and furthermore, a carbonized layer (char) of the flame retardant It is considered that by promoting the formation of, an excellent flame retardant effect is exhibited. In particular, in the case of the flame retardant B, it is essential to use it together with the inorganic filler.

As the inorganic filler, known resin fillers can be used, for example, mica, kaolin, talc, silica, clay, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, glass beads, glass balloon, Glass flake, glass fiber, fibrous alkali metal titanate (potassium titanate fiber, etc.), fibrous transition metal borate (aluminum borate fiber, etc.), fibrous alkaline earth metal borate (magnesium borate fiber, etc.) ), Zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, gypsum whisker, aluminum silicate (mineral name mullite) whisker, calcium silicate (mineral name wollastonite) whisker, silicon carbide whisker, titanium carbide whisker, silicon nitride whisker, nitriding Titanium whis Chromatography, carbon fibers, alumina fibers, alumina - silica fibers, mention may be made of zirconia fibers, quartz fibers.

Among these inorganic fillers, fibrous alkali metal titanate, fibrous transition metal borate, fibrous alkaline earth metal borate, zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, aluminum silicate whisker, calcium silicate Preferred are whiskers, silicon carbide whiskers, titanium carbide whiskers, silicon nitride whiskers, fibrous materials such as titanium nitride whiskers, and those having shape anisotropy such as mica, and fibrous alkali metal titanates and fibrous transition metal borate salts. Particularly, fibrous alkaline earth metal borate, titanium oxide whiskers, calcium silicate whiskers and the like are particularly preferable.

These inorganic fillers can be used alone or in combination of two or more.

中 で も Among these inorganic fillers, those having shape anisotropy such as whiskers and mica can be preferably used.

The potassium titanate fiber, which is one of the inorganic fillers, usually has an average fiber diameter of about 0.05 to 2.0 μm, an average fiber length of about 1 to 500 μm, and preferably has an aspect ratio (fiber length / fiber Potassium hexatitanate fiber having a diameter of 10 or more. Among these, potassium hexatitanate fibers having a pH of 6.0 to 8.5 are particularly preferred. Here, the pH of the potassium titanate fiber refers to a pH value measured at 20 ° C. after stirring a 1.0 wt% suspension of potassium titanate fiber (using deionized water) for 10 minutes. If the pH of the potassium titanate fiber greatly exceeds 8.5, the physical properties of the resin and the heat discoloration resistance may decrease, which is not preferable. On the other hand, when the pH is extremely lower than 6.0, not only is the effect of improving the strength of the obtained resin composition reduced, but also the residual acid causes corrosion of the processing machine and the mold, which is not preferable. .

The mixing ratio of the inorganic filler to the thermoplastic resin or the thermosetting resin is not particularly limited, but in consideration of the balance between the improvement of the mechanical properties and the improvement of the flame retardancy, the thermoplastic resin or the thermosetting resin is usually used. The amount is preferably 0.01 to 50 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of the curable resin.

(d) Organic phosphorus compound not containing halogen In order to further improve the flame retardancy of the flame-retardant resin composition of the present invention, an organic phosphorus compound containing no halogen (hereinafter referred to as “halogen-free organic phosphorus compound”) ).

Conventionally, it is known that halogen-free organic phosphorus compounds improve the flame retardancy of a matrix such as a resin. However, the present inventor has found that when the specific phosphazene compound used in the present invention and the halogen-free organic phosphorus compound are used in combination, a synergistic effect is exhibited and the flame retardant effect is significantly enhanced. Although the reason why such a remarkable effect is achieved is not yet sufficiently clear, the combined use of the two forms a carbonized layer on the surface of the resin composition, forms an expanded layer, and decomposes both layers during combustion. This is probably because the diffusion and heat transfer of the product were suppressed.

従 来 As the halogen-free organic phosphorus compound, conventionally known compounds can be widely used. For example, those described in JP-B-6-19003, JP-A-2-115262, JP-A-5-1079, JP-A-6-322277, U.S. Pat. No. 5,122,556 and the like can be mentioned. .

More specifically, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, tolyl dixylyl phosphate, tris ( (Norylphenyl) phosphate, phosphate ester such as (2-ethylhexyl) diphenyl phosphate, hydroxyl group-containing phosphate ester such as resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bisphenol-A Bis (diphenyl phosphate), bisphenol-Sbis ( Phenyl phosphate), resorcinol bis (dixylyl phosphate), hydroquinone bis (dixylyl phosphate), bisphenol-A bis (ditolyl phosphate), biphenol-A bis (dixylyl phosphate), bisphenol-S bis (dixylyl phosphate), etc. And a phosphine or phosphine oxide compound such as trilauryl phosphine, triphenyl phosphine, tolyl phosphine, triphenyl phosphine oxide, and tolyl phosphine oxide.

Among these halogen-free organic phosphorus compounds, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bisphenol-A bis (diphenyl phosphate), resorcinol bis (dixylyl) Phosphate), condensed phosphoric acid ester compounds such as hydroquinone bis (dixylyl phosphate), bisphenol-A bis (ditolyl phosphate), and phosphine oxide compounds such as triphenylphosphine oxide and tolylphosphine oxide, and particularly preferred are triphenylphosphate , Resorcinol bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate), Le phosphine oxide and the like are preferable.

The halogen-free organic phosphorus compound can be used alone or in combination of two or more.

The halogen-free organic phosphorus compound is particularly effective when used in combination with the flame retardant A or the flame retardant B.

The blending ratio of the halogen-free organic phosphorus compound to the thermoplastic resin or the thermosetting resin is not particularly limited. However, in consideration of the balance between the improvement in mechanical properties and the improvement in flame retardancy, a thermoplastic resin is usually used. Alternatively, the amount is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight per 100 parts by weight of the thermosetting resin. In this case, the proportion of the flame retardant is usually 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin or the thermosetting resin.

(e) Fluororesin Further, the flame retardant resin composition of the present invention using a thermoplastic resin as a matrix may contain a fluororesin within a range that does not impair the object of the present invention. The blending amount is not particularly limited, but is usually 0.01 to 2.5 parts by weight, preferably 0.1 to 1.2 parts by weight per 100 parts by weight of the thermoplastic resin.

As the fluororesin, conventionally known ones can be widely used, for example, polytetrafluoroethylene resin (PTFE), ethylene tetrafluoride-propylene hexafluoride copolymer resin (FEP), ethylene tetrafluoride-perfluoroalkyl vinyl ether Copolymer resin (PFA), ethylene tetrafluoride-ethylene copolymer resin (ETFE), poly (chlorotrifluoroethylene) resin (CTFE), polyvinylidene fluoride (PVdF) and the like can be mentioned, and PTFE is particularly preferable. is there. By the addition of the fluororesin, the drip prevention effect is further exhibited.

The combination of the fluororesin and the flame retardant A is particularly effective.

(f) Other additives The flame-retardant resin composition of the present invention does not use a compound containing halogen such as chlorine or bromine as a flame-retardant component, and exhibits an excellent flame-retardant effect. However, it is also possible to add a commonly used known flame retardant additive in an appropriate combination as long as the excellent effect is not impaired.

Additives for flame retardancy are not particularly limited as long as they exhibit a flame retardant effect, and metal oxides such as zinc oxide, tin oxide, iron oxide, molybdenum oxide, copper oxide, and manganese dioxide Metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide treated with oxalic acid, magnesium hydroxide treated with a nickel compound, sodium carbonate, calcium carbonate, barium carbonate, sodium alkyl sulfonate, etc. Organic chlorine compounds such as alkali metal salts or alkaline earth metal salts, chlorinated paraffins, perchlorocyclopentadecane, tetrabromobisphenol-A, epoxy resins, bis (tribromophenoxy) ethane and bis (tetrabromophthalimino) ethane Or organic bromine compounds, antimony trioxide, Zimon, antimony pentoxide, antimony compounds such as sodium antimonate, red phosphorus, halogen-containing phosphate compound, halogen-containing condensed phosphate compound or phosphonate compound, melamine, melamine cyanurate, melamine phosphate, melam, melem, Nitrogen-containing compounds such as melon, succinoguanamine, guanidine sulfamate, ammonium sulfate, ammonium phosphate, ammonium polyphosphate, alkylamine phosphate, boron compounds such as zinc borate, barium metaborate, and ammonium borate, silicone polymers, silica, etc. And a heat-expandable graphite.

は One of these additives for flame retardancy can be used alone, or two or more can be used in combination.

耐熱 The heat resistance and flame retardancy of the resin can be further improved by adding a small amount of Lewis acid to the flame retardant resin composition containing the flame retardant C of the present invention. As the Lewis acid, conventionally known ones can be widely used, and examples thereof include zinc chloride and iron chloride. These Lewis acids can be used alone or in combination of two or more. Further, these Lewis acids are preferably blended usually in an amount of about 0.01 to 0.6 parts by weight based on the total amount of the flame-retardant resin composition.

Further, the flame-retardant resin composition of the present invention may be appropriately combined with various conventionally known resin additives as long as the excellent properties are not impaired. Examples of the resin additive include a flame retardant other than the above, an anti-drip agent (anti-drip agent), an ultraviolet absorber, a light stabilizer, an antioxidant, a light-blocking agent, a metal deactivator, a quencher, a heat stabilizer, Lubricants, release agents, coloring agents, antistatic agents, anti-aging agents, plasticizers, impact strength improvers, compatibilizers and the like can be mentioned.

The ultraviolet absorber absorbs light energy and becomes a keto-type molecule through intramolecular proton transfer (benzophenone, benzotriazole-based) or cis-trans isomerization (cyanoacrylate-based), thereby causing thermal absorption. It is a component to release and detoxify as energy. Specific examples thereof include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 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 droxy-3 ', 5'-dicumylphenyl) benzotriazole and 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'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide, and ethyl-α-cyano-β, β-diphenylacrylate And cyano such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Relate, and the like can be mentioned.

The light stabilizer is a component for decomposing hydroperoxide generated by light energy to generate stable NO—radicals, N—OR, and N—OH, and is a component for stabilization. For example, a hindered amine light stabilizer Can be mentioned. Specific examples thereof include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 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, 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) di (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 polycondensation product, 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.

防止 Antioxidant is a component for stabilizing generated peroxide radicals such as hydroperoxy radicals or decomposing generated peroxides such as hydroperoxides by thermoforming or light exposure. Examples of the antioxidant include a hindered phenol-based antioxidant and a peroxide decomposer. The former acts as a radical chain inhibitor, and the latter acts to decompose peroxides generated in the system into more stable alcohols to prevent autoxidation.

Examples of hindered phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, styrenated phenol, n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl Phenyl 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 [methyle 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl)- Propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

Examples of the peroxide decomposer include organic phosphorus peroxide decomposers such as tris (nonylphenyl) phosphite, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and dilauryl- 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl Organic sulfur-based peroxide decomposers such as -3,3'-thiodipropionate and 2-mercaptobenzimidazole can be exemplified.

The light blocking agent is a component for preventing light from reaching the polymer bulk. Specific examples 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 deactivating heavy metal ions in the resin by a chelate compound. Specific examples thereof include benzotriazole and its derivatives (specifically, 1-hydroxybenzotriazole and the like).

The quencher is a component for deactivating a functional group such as a photo-excited hydroperoxide or a carbonyl group in a polymer by energy transfer, and specific examples thereof include organic nickel.

従 来 Further, for the purpose of imparting antifogging property, antifungal property, antibacterial property, or other functions, various conventionally known additives may be further added.

Production of Flame-Retardant Resin Composition of the Present Invention The flame-retardant resin composition of the present invention comprises a thermoplastic resin or a thermosetting resin, the above-described flame retardant and, if necessary, an inorganic filler, a halogen-free organic phosphorus compound, and a fluororesin. It can be obtained by weighing and adding a predetermined amount or an appropriate amount of various additives for flame retardation and other additives, and mixing and kneading by a known method. For example, a mixture of each component in the form of powder, beads, flakes, or pellets is kneaded using an extruder such as a single-screw extruder, a twin-screw extruder, a kneader such as a Banbury mixer, a pressure kneader, or a two-roll extruder. By doing so, the resin composition of the present invention can be obtained. When it is necessary to mix a liquid, the mixture can be kneaded with the above-described extruder or kneader using a known liquid injection device.

The flame-retardant resin molded article of the present invention By molding the flame-retardant resin composition of the present invention, a flame-retardant resin molded article can be obtained. For example, extruded products of various shapes such as resin plates, sheets, films, and deformed products can be manufactured by conventionally known molding means such as press molding, injection molding, and extrusion molding. It is also possible to manufacture a resin plate having a two-layer or three-layer structure using the method described above.

The flame-retardant resin composition and the flame-retardant resin molded product of the present invention obtained as described above are used for electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, and rubber. It can be used in a wide range of industrial fields such as leather, automobile, precision equipment, wood, furniture, printing, musical instruments, etc.

More specifically, the flame-retardant resin composition and the flame-retardant resin molded article of the present invention can be used for a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a facsimile, a copier, an ECR (electronic Office / OA equipment such as calculators, electronic organizers, electronic dictionaries, electronic dictionaries, cards, holders, stationery, etc., home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu, etc. , TV, VTR, video camera, boombox, tape recorder, mini disk, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, capacitor, switch, printed circuit board, coil bobbin, semiconductor sealing material, electric wire, cable, It is used for applications such as electric and electronic parts such as transformers, deflection yokes, distribution boards and watches, and communication equipment.

Further, the flame-retardant resin composition and the flame-retardant resin molded article of the present invention can be used for seats (filling, dress material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors. , Foil covers, mattress covers, airbags, insulating materials, suspenders, suspenders, electric wire covering materials, electric insulating materials, paints, coating materials, overlays, flooring, corner walls, deck panels, covers, plywood , Ceiling, partition, side wall, carpet, wallpaper, wall covering, exterior, interior, roof, soundproofing, heat insulation, window, etc., automobile, vehicle, ship, aircraft and building materials, clothing , Curtains, sheets, plywood, plywood, carpets, doormats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments, etc. Ports are used in products for various applications.

合成 The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

Synthesis Example 1 (Compound A; Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure with Paraphenylene)
2.04 mol (196 g) of phenol and the same mol (82 g) of sodium hydroxide were azeotropically dehydrated with toluene to prepare about 1200 g of a 20% solution of sodium phenolate in toluene.

In parallel with the above reaction, dichlorophosphazene oligomer (58.57% trimer, 12.26% tetramer, 11.11% pentamer and hexamer, 2.82% heptamer, octamer 580 g of a 20% chlorobenzene solution containing 115.9 g of the above mixture (12.04%) was placed in a two-liter four-necked flask, and 0.15 mol (18.3 g) of hydroquinone dilithium salt separately prepared under stirring. ) Was added dropwise. After the dropwise addition, the mixture was stirred and reacted at 50 ° C. for 5 hours. Subsequently, about 1200 g of a 20% toluene solution of sodium phenolate prepared above was added dropwise with stirring, and the mixture was stirred and reacted at 100 ° C. for 8 hours.

After the reaction was completed, the reaction mixture was concentrated, poured into 3 liters of a mixed solvent of water / methanol = 1/1 by volume under stirring, neutralized with dilute sulfuric acid, and filtered. Next, the mixture was washed twice with 3 liters of a mixed solvent of water / methanol = 1/1 by volume, filtered, and dried under vacuum at 80 ° C. and 20 mmHg for 11 hours to obtain 220 g of a slightly yellow powder.

The crosslinked phenoxyphosphazene compound obtained above did not show a clear melting point, and the decomposition start temperature by TG / DTA analysis was 305 ° C. Also, from the phosphorus content and the CHN elemental analysis value, the composition of the crosslinked phenoxyphosphazene compound may be approximately [N = P (-Op-Ph-O-) _0.15 (-O-Ph) _1.7 ]. found.

Synthesis Example 2 (Compound B: Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure with 2,2-Bis (p-oxyphenyl) propane Group)
86.7 g (0.38 mol) of bisphenol-A and 460 ml of tetrahydrofuran (THF) are placed in a two-liter four-necked flask, and 3.5 g of metal Li (0.degree. (0.5 mol). After completion of the charging, the temperature was raised to 61 ° C. over 1 hour, and stirring was continued at 61 ° C. to 68 ° C. for 4 hours. After completion of the reaction, the lithium salt of bisphenol-A in the reaction mixture became a white slurry.

215.6 g (2.25 mol) of phenol and 500 ml of toluene were placed in a three-liter four-necked flask, and 34.5 g (1.5 mol) of metal Na was added with stirring while maintaining the internal liquid temperature at 25 ° C. It was cut and put. After completion of the charging, the temperature was raised to 77 ° C. over 4 hours, and stirring was continued at 77 ° C. to 113 ° C. for 3 hours. After completion of the reaction, sodium phenolate of the reaction mixture became a white slurry.

Dichlorophosphazene oligomer (concentration 37.01%, monochlorobenzene solution, trimer 58.57%, tetramer 12.26%, 5 and hexamer 11.11%, heptamer 2.82%, 8 313.13 g (1.0 mol) in a 5 liter four-necked flask, and while stirring, while maintaining the internal liquid temperature at 20 ° C., lithium lithium of bisphenol-A The salt solution was added dropwise over 1 hour. The contents became pale yellow milky. Then, while stirring, the sodium phenolate solution was added dropwise over 1 hour while maintaining the internal liquid temperature at 20 ° C. The contents became a brown slurry. After completion of the dropwise addition, stirring was continued at 47 ° C. for 13 hours. It became a light brown slurry.

後 After the completion of the reaction, the reaction mixture was concentrated. Then, the mixture was washed three times with 3% of 2% NaOH, filtered, washed three times with 3 liters of a mixed solvent of water / methanol = 1/1, filtered, and dried under vacuum at 80 ° C. and 20 mmHg for 11 hours. A powder was obtained. Yield 208.67 g, 86.50% based on dichlorophosphazene.

The obtained compound had a hydrolyzed chlorine content of 0.93%, a decomposition temperature of 296.0 ° C, and a 5% weight loss temperature of 307.7 ° C. The composition of the phosphorus content and the final product from the CHN elemental analysis value was [N = P (-O-Ph -C (CH 3) 2 -Ph-O-) 0.25 (-O-Ph) 1.50].

Synthesis Example 3 (Compound C: Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure with Metaphenylene)
Using resorcinol instead of hydroquinone, a reaction and treatment were carried out in the same manner as in Synthesis Example 1 to obtain a white powder having a composition of [N = P (-Om-Ph-O-) _0.15 (-O-Ph) _1.7 ]. Obtained. This crosslinked phenoxyphosphazene compound did not show a clear melting point, and the decomposition start temperature by TG / DTA analysis was 300 ° C.

Example 1
To a resin consisting of 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin, 15 parts of the compound A produced in Synthesis Example 1 and 0.2 parts of PTFE are added, mixed with a mixer, and then melt-kneaded using a Labo Plastomill. Thus, a flame-retardant resin composition was obtained.

A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and the flame retardancy was evaluated based on the UL-94 test method and the heat distortion temperature was measured according to ASTM D-648. Was. As a result, the flame retardancy was V-0 and the heat distortion temperature was 108 ° C., and no juicing was observed during molding.

Example 2
A sample was prepared and evaluated in the same manner as in Example 1, except that the compound B produced in Synthesis Example 2 was used instead of the compound A. As a result, the flame retardancy was V-0 and the heat distortion temperature was 111 ° C., and no juicing was observed during molding.

Example 3
A sample was prepared and evaluated in the same manner as in Example 1, except that the compound C prepared in Synthesis Example 3 was used instead of the compound A. As a result, the flame retardancy was V-0 and the heat distortion temperature was 106 ° C., and no juicing was observed during molding.

Example 4
A sample was prepared in the formulation of Example 1 without adding PTFE, and the flame retardancy and the heat distortion temperature were evaluated. As a result, the flame retardancy was V-0 and the heat distortion temperature was 109 ° C., and no juicing was observed during molding.

Comparative Example 1
A sample was prepared and evaluated in the same manner as in Example 1, except that trixylyl phosphate was used in place of compound A. As a result, the flame retardancy was V-2 and the heat distortion temperature was 82 ° C., and juicing was observed during molding.

Reference Example 1
460 g (3 mol) of phosphorus oxychloride, 110 g (2 mol) of resorcin, 94.1 g (1 mol) of phenol and 9 g (catalyst) of aluminum chloride were simultaneously charged into a stirring rod, a condenser, a dropping funnel and a flask equipped with a thermometer at 150 ° C. And then reacted by adding 564.6 g (6 mol) of phenol. After washing the reaction mixture with water, triphenyl phosphate was distilled off under a high-temperature vacuum to obtain 515 g of condensed phosphoric acid diphenyl ester crosslinked with resorcinol.

品質 Quality of this condensed phosphoric acid diphenyl ester: yellow liquid, average molecular weight = 540,% P = 10.6, acid value 2.2.

Comparative Example 2
A sample was prepared and evaluated in the same manner as in Example 1, except that the condensed phosphoric acid diphenyl ester crosslinked with resorcinol (obtained in Reference Example 1) was used instead of Compound A. As a result, the flame retardancy was V-2 and the heat distortion temperature was 89 ° C., and juicing was observed during molding.

Comparative Example 3
When a sample was prepared and evaluated in the same manner as in Example 1 without adding a flame retardant, the test piece burned, and showed no flame retardancy. The heat distortion temperature was 111 ° C.

Example 5
To a resin consisting of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene, 15 parts of compound A is added and mixed with a mixer. To obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and the flame retardancy was evaluated based on the UL-94 test method and the heat distortion temperature was measured according to ASTM D-648. Was. As a result, the flame retardancy was V-0 and the heat distortion temperature was 130 ° C., and no juicing was observed during molding.

Example 6
A sample was prepared and evaluated in the same manner as in Example 5, except that Compound B was used instead of Compound A. As a result, the flame retardancy was V-0 and the heat deformation temperature was 131 ° C., and no juicing was observed during molding.

Example 7
A sample was prepared and evaluated in the same manner as in Example 5, except that Compound C was used instead of Compound A. As a result, the flame retardancy was V-0 and the heat distortion temperature was 128 ° C., and no juicing was observed during molding.

Comparative Example 4
A sample was prepared and evaluated in the same manner as in Example 5, except that triphenyl phosphate was used in place of compound A. As a result, the flame retardancy was V-2 and the heat distortion temperature was 110 ° C., and juicing was observed during molding.

Comparative Example 5
A sample was prepared and evaluated in the same manner as in Example 5, except that the condensed phosphoric acid diphenyl ester crosslinked with resorcinol (obtained in Reference Example 1) was used instead of Compound A. As a result, the flame retardancy was V-2 and the heat deformation temperature was 115 ° C., and juicing was observed during molding.

Comparative Example 6
When a sample was prepared and evaluated in the same manner as in Example 5 without adding a flame retardant, the test piece burned, and showed no flame retardancy. The heat distortion temperature was 133 ° C.

Example 8
A varnish was prepared by adding 10 parts of compound A to 100 parts of a bisphenol-A type epoxy resin, and impregnated with glass cloth and dried to prepare a prepreg. Subsequently, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, which was cut into a specified size to obtain a test piece. Using this test piece, flame retardancy was evaluated based on the UL-94 test method, and as a result, flame retardancy V-0 was obtained. No juicing was observed during hot pressing.

Example 9
A sample was prepared and evaluated in the same manner as in Example 8, except that Compound C was used instead of Compound A. As a result, the flame retardancy was V-0, and no juicing was observed during hot pressing.

Comparative Example 7
A sample was prepared and evaluated in the same manner as in Example 8, except that the condensed phosphoric acid diphenyl ester crosslinked with resorcinol (obtained in Reference Example 1) was used instead of Compound A. As a result, the flame retardancy was V-2, and juicing was observed during hot pressing.

Comparative Example 8
When a sample was prepared and evaluated in the same manner as in Example 8 without adding a flame retardant, the test piece burned, and showed no flame retardancy.

Examples 10 to 13
General formula-[-N = P (-O-crosslinking group -O-) x (-O-Ph) y-] n- synthesized in the same manner as in Synthesis Example 2.
A flame retardancy test was conducted in the same manner as in Example 1 using the compound represented by Table 1 shows the results.

In Table 1, Tm (° C.) is the melting temperature by thermogravimetric analysis (TG / DTA analysis), T5 (° C.) is the temperature of 5% weight loss by thermogravimetric analysis, and Td (° C.) is the decomposition temperature by thermogravimetric analysis. It is.

よ う As is clear from Table 1, the moldability of each of the resin compositions containing the flame retardant comprising the compound represented by the above general formula was good, and no juicing was observed.

Synthesis Example 4 (Compound D: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-Sulfonyldiphenylene (Bisphenol-S Residue))
In a 1-liter four-necked flask, 1.28 mol (121.14 g) of phenol and 0.017 mol (4.26 g) of bisphenol-S are dissolved in 500 ml of tetrahydrofuran (THF), and metal sodium crushed at 25 ° C. or lower. 7.6 g was added, and after the addition was completed, the temperature was raised to 61 ° C. over 1 hour, and stirring was continued at 61 ° C. to 68 ° C. for 6 hours to prepare a sodium phenolate mixed solution.

In parallel with the above reaction, dichlorophosphazene oligomers (58.57% of trimers, 12.26% of tetramers, 11.11% of 5, and hexamers, 2.82% of heptamers, 2.8% or more of octamers and 12 In a 2 liter four-necked flask, 290 g of a 20% chlorobenzene solution containing 0.5 unit mol (58 g) was prepared, and cooled and stirred at 25 ° C. or lower. Was added dropwise. After dropping, the mixture was stirred and reacted at 71 to 73 ° C for 15 hours.

After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 ml of chlorobenzene, washed three times with a head, washed with 5% aqueous NaOH, washed with 5% sulfuric acid, washed with 5% aqueous sodium bicarbonate, and washed with water three times, and concentrated to dryness. This gave 108 g of a pale yellow wax. Yield 93.5%.

Its weight average molecular weight (Mw) by GPC analysis is 810 in terms of polystyrene, its melting temperature (Tm) by TG / DTA analysis is 103 ° C., its 5% weight loss temperature (T5) and its decomposition onset temperature (Td) 330 and 347 ° C., respectively.

Also, the residual chlorine content is 0.09%, from phosphorus content and CHN elemental analysis data, the composition of this object substantially [N = P (-O-Ph -SO 2 -Ph-O-) 0.025 (- O-Ph) _1.95 ].

Synthesis Examples 5 to 6 (Compound E and Compound F: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure Using 4,4′-Sulfonyldiphenylene (Bisphenol-S Residue))
1.254 mol (118.03 g) of phenol and 0.033 mol (8.26 g) of bisphenol-S [or 1.122 mol (105.60 g) of phenol and 0.099 mol (24.77 g) of bisphenol-S] The reaction and post-treatment were carried out in the same manner as in Synthesis Example 4 to obtain a pale yellow wax-like substance. As a result of analysis, the following compounds were confirmed.
Compound E:
[N = P (-O-Ph -SO 2 -Ph-O-) 0.05 (-O-Ph) 1.90]
Yield 91.5%, residual chlorine = 0.01% or less, Mw = 820, Tm = 103 ° C., T5 = 332 ° C., Td = 347 ° C.
Compound F:
[N = P (-O-Ph -SO 2 -Ph-O-) 0.15 (-O-Ph) 1.70]
Yield 90.0%, residual chlorine = 0.11%, Mw = 850, Tm = 102 ° C., T5 = 333 ° C., Td = 355 ° C.

Synthesis Examples 7 and 8 (Compound G and Compound H: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-Oxydiphenylene Group)
Bis (4-hydroxyphenyl) ether 13.4 g (0.066 mol) and phenol 111.7 g (1.188 mol) [or bis (4-hydroxyphenyl) ether 26.8 g (0.132 mol) and phenol 99 0.3 g (1.056 mol)] and 27.6 g (1.2 mol) of metallic Na, the same reaction and treatment were carried out on the same scale as in Synthesis Example 4 to obtain the following highly viscous compounds.
Compound G:
[N = P (-O-Ph-O-Ph-O-) _0.1 (-O-Ph) _1.8 ]
Yield 99.8%, residual chlorine = 0.01% or less, Mw = 1510, Tm = not detectable, T5 = 346 ° C., Td = 353 ° C.
Compound H:
[N = P (-O-Ph-O-Ph-O-) _0.2 (-O-Ph) _1.6 ]
Yield 97.9%, residual chlorine = 0.11%, Mw = 1950, Tm = not detectable, T5 = 318 ° C., Td = 375 ° C.

Synthesis Examples 9 to 10 (Compound I and Compound J: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-thiodiphenylene Group)
Using 14.4 g (0.066 mol) of 4,4'-thiodiphenol [or 28.8 g (0.132 mol)], the reaction and treatment were carried out in the same manner as in Synthesis Examples 7 and 8, and the following high viscosity was obtained. The compound was obtained.
Compound I:
[N = P (-O-Ph-S-Ph-O-) _0.1 (-O-Ph) _1.8 ]
Yield 98.8%, residual chlorine = 0.09%, Mw = 1690, Tm = not detectable, T5 = 340 ° C., Td = 344 ° C.
Compound J:
[N = P (-O-Ph-S-Ph-O-) _0.2 (-O-Ph) _1.6 ]
Yield 95.1%, residual chlorine = 0.01%, Mw = 3050, Tm = not detectable, T5 = 344 ° C., Td = 348 ° C.

Synthesis Examples 11 to 12 (Compound K and Compound L: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-Diphenylene Group)
Using 12.3 g (0.066 mol) of 4,4'-diphenol [or 24.6 g (0.132 mol)], the reaction and treatment were carried out in the same manner as in Synthesis Examples 7 and 8, and the following highly viscous compound was obtained. Got.
Compound K:
[N = P (-O-Ph-Ph-O-) _0.1 (-O-Ph) _1.8 ]
Yield 99.9%, residual chlorine = 0.01%, Mw = 1590, Tm = not detectable, T5 = 348 ° C., Td = 349 ° C.
Compound L:
[N = P (-O-Ph-Ph-O-) _0.2 (-O-Ph) _1.6 ]
Yield 97.0%, residual chlorine = 0.11%, Mw = 1900, Tm = not detectable, T5 = 345 ° C., Td = 347 ° C.

Example 14
A resin consisting of 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin is mixed with 15 parts of phenoxyphosphazene (compound D) having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol-S residue) and 0.5 part of PTFE. Was added and mixed with a mixer, followed by melt-kneading using a Labo Plastmill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and the flame retardancy was evaluated based on the UL-94 test method and the heat distortion temperature was measured according to ASTM D-648. Was. As a result, there was no dripping of the test piece, the flame retardancy was V-0 and the heat deformation temperature was 111 ° C., and no juicing was observed during molding.

Example 15
Using 18 parts of Compound E, a sample was prepared and evaluated in the same manner as in Example 14 without adding PTFE. As a result, there was no melting dripping that ignites the cotton of the test piece, the flame retardancy was V-0, the heat deformation temperature was 112 ° C., and no juicing was observed during molding. From this result, it was confirmed that the compound was a compound capable of exhibiting desired flame retardancy without using PTFE, and proved to be a true non-halogen flame retardant.

Examples 16 to 22
Using Compounds F to L, sample preparation and evaluation were performed in the same manner as in Example 13. Table 2 shows the results.

Example 23
To a resin consisting of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene, 15 parts of phenoxyphosphazene having a crosslinked structure of compound E is added and mixed with a mixer. Using a Labo Plastmill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a heat press, and the flame retardancy was evaluated based on the UL-94 V test method and the heat distortion temperature was measured according to ASTM D-648. went. As a result, the flame retardancy was V-0 and the heat deformation temperature was 131 ° C., and no juicing was observed during molding.

Example 24
A sample was prepared and evaluated in the same manner as in Example 23, except that Compound H was used instead of Compound E. As a result, the flame retardancy was V-0 and the heat deformation temperature was 133 ° C., and no juicing was observed during molding.

Example 25
A sample was prepared and evaluated in the same manner as in Example 23, except that Compound J was used instead of Compound E. As a result, the flame retardancy was V-0 and the heat distortion temperature was 130 ° C., and no juicing was observed during molding.

Example 26
A varnish was prepared by adding 10 parts of Compound D to 100 parts of a bisphenol-A type epoxy resin, and impregnating the same with a glass cloth, followed by drying to prepare a prepreg. Next, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, and cut into prescribed dimensions to obtain test pieces. Using this test piece, flame retardancy was evaluated based on the UL-94 test method, and as a result, flame retardancy V-0 was obtained. No juicing was observed during hot pressing.

Example 27
A sample was prepared and evaluated in the same manner as in Example 26, except that Compound H was used instead of Compound E. As a result, the flame retardancy was V-0, and no juicing was observed during hot pressing.

Example 28
A sample was prepared and evaluated in the same manner as in Example 26, except that Compound J was used instead of Compound E. As a result, the flame retardancy was V-0, and no juicing was observed during hot pressing.

Synthesis Example 13 (Synthesis of chlorphosphazene)
2512 g (12 mol) of 99.5% phosphorus pentachloride (PCl ₅ ), 688 g (12.8 mol) of 99.5% ammonium chloride (NH ₄ Cl), 20 g (0.10 g) of 97.0% zinc chloride (ZnCl ₂ ). 16 mol) and 5 liters of monochlorobenzene (MCB) are placed in a reaction vessel equipped with a temperature controller, a stirrer and a reflux device, and the reaction is started at 24 ° C. at first, gradually heated, and 3 hours after the start of the reaction To 130 ° C. After further refluxing at 130 ° C. to 134 ° C. for 2 hours with stirring, the reaction mixture was filtered to remove 76 g of a white filtration residue, and 6883 g of chlorphosphazene (100% chlorophosphazene conversion) as a nearly colorless and transparent MCB solution. 1343 g, chlorphosphazene concentration in the solution was 19.51%). 96.56% yield (vs. phosphorus pentachloride).

As a result of analysis by ³¹ P-NMR, trimer m = 3 (where m represents m in the above general formula): 54%, tetramer m = 4: 19%, pentamer m ≧ 5: 27%.

This solution was concentrated to give a 39.5% chlorphosphazene solution, which was used as a raw material for Synthesis Example 14.

Synthesis Example 14 (Synthesis of phenoxyphosphazene)
2931 g (31.14 mol) of phenol (PhOH), 596.67 g (25.95 mol) of metal Na and 7 liter of tetrahydrofuran (THF) were placed in a reaction vessel equipped with a temperature controller, a stirrer and a reflux device, and stirred. Refluxed for 8 hours. The reaction mixture is slightly colored. Next, a solution obtained by dissolving the 39.5% chlorphosphazene solution (3172.41 g) obtained in Synthesis Example 13 in 5.5 L of THF was added dropwise to this solution at a temperature of 42 ° C to 79 ° C. After completion of the dropwise addition, reflux was continued at 78 ° C. for 10 hours with stirring.

Next, the reaction mixture was concentrated and dissolved in 8 liters of monochlorobenzene, 5 liters of water, and 3 liters of a 5% aqueous NaOH solution. This was washed in the following order. Two times with 7 liters of 5% NaOH aqueous solution, once with 7 liters of 5% hydrochloric acid, once with 7 liters of 7% NaHCO3 aqueous solution, and twice with 7 liters of water. After washing, MgSO ₄ was added, dried and concentrated. Finally, vacuum drying was performed at 80 ° C. and 3 torr or less for 12 hours to obtain 2437 g of yellow sherbet-like phenoxyphosphazene. Yield 97.5%.

The analysis results are as follows. ^{From 31} P-NMR, trimer m = 3: 55%, tetramer m = 4: 18%, pentamer m ≧ 5: 27%, weight average molecular weight Mw = 720 by GPC, mp = 109 ° C. 5% weight loss temperature Td (5%) = 343 ° C., decomposition temperature Td = 366 ° C., residue after pyrolysis (600 ° C.) = 19%, residual PhOH = 0.038 wt%, residual MCB = 0.042 wt%, Residual chlorine = 0.102%.

Example 29
A resin consisting of 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin, 15 parts of phenoxyphosphazene obtained in Synthesis Example 14 as a flame retardant and potassium titanate fiber (trade name: TISMO N-102, manufactured by Otsuka Chemical Co., Ltd.) The same was applied hereinafter), and 7.5 parts were added, mixed by a mixer, and then melt-kneaded by using a Labo Plastomill to obtain a flame-retardant resin composition.

試 験 A test having a thickness of 1/16 inch was prepared from this composition by a hot press, and the flame retardancy was evaluated based on the UL-94 test method, and the heat distortion temperature was measured according to ASTM D-648. Further, at the time of the flame retardancy test, the presence or absence of flaming particles (drip) that ignite cotton, the presence or absence of generation of volatile gas during kneading of Labo Plastomill, and the change in appearance after molding of the test piece were examined. Table 3 shows the results.

Examples 30 to 31
In Example 29, it replaced with potassium titanate fiber, and carried out similarly to Example 29 except having used kaolin (Wako Pure Chemical Industries, Ltd. reagent) or mica (brand name: Clarite Mica 400W, Kuraray Co., Ltd.). Thus, a flame-retardant resin composition was obtained. The flame retardancy of these compositions was evaluated in the same manner as in Example 29. Table 3 shows the results.

Examples 32 to 35
In Example 29, a flame-retardant resin composition was obtained in the same manner as in Example 29 except that compounds E to H were used instead of phenoxyphosphazene of Synthesis Example 2. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Example 36
In Example 29, a resin composed of 60 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 40 parts of rubber-modified impact-resistant polystyrene was used instead of the resin composed of the polycarbonate resin and the ABS resin. Except that, a flame-retardant resin composition was obtained in the same manner as in Example 29. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Example 37
A varnish was prepared by adding 15 parts of the phenoxyphosphazene synthesized in Synthesis Example 14 and 7.5 parts of potassium titanate fiber to 100 parts of the bisphenol-A type epoxy resin, impregnating the varnish with a glass cloth, and then drying. To prepare a prepreg. Subsequently, a predetermined number of the prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, which was cut into a specified size to obtain a test piece. Using this test piece, a combustion test based on the UL-94 test method and a measurement of the heat distortion temperature were performed according to the above-described methods. Table 3 shows the results.

Comparative Example 9
A resin composition was obtained in the same manner as in Example 29 except that the potassium titanate fiber was not blended. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Comparative Example 10
A resin composition was obtained in the same manner as in Example 36 except that potassium titanate fiber was not blended. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Comparative Example 11
A resin composition was obtained in the same manner as in Example 37 except that the potassium titanate fiber was not blended. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Synthesis Example 15 (Synthesis of phenoxyphosphazene having 4-cyanophenoxy group)
0.44 mol (52.4 g) of 4-cyanophenol, 2.20 mol (207.0 g) of phenol and hydroxylation in a two-liter four-necked flask equipped with a stirrer, a heating device, a thermometer and a dehydrator. 2.64 mol (105.6 g) of sodium and 1000 ml of toluene were added. The mixture was heated to reflux to remove water from the system, and a toluene solution of cyanophenol and sodium salt of phenol was prepared.

1 unit mol (115.9 g) of dichlorophosphazene oligomer (trimer 59%, tetramer 12%, 5 and hexamer 11%, heptamer 3) was added to this toluene solution of cyanophenol and the sodium salt of phenol. %, 580 g of a 20% chlorobenzene solution containing an octamer or more cyclic and linear compound (15%) was added dropwise at an internal temperature of 30 ° C. or lower while stirring. After the mixed solution was refluxed for 12 hours, a 5% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was washed twice. Next, the organic layer was neutralized with dilute sulfuric acid, washed twice with water, filtered, concentrated and dried under vacuum (vacuum drying conditions: 80 ° C., 5 mmHg, 12 hours) to obtain 220 g of a slightly yellow viscous liquid. Got. The yield calculated from the dichlorophosphazene oligomer used was 92%.

The residual hydrolyzable chlorine in the product was 0.09%, the ¹ H-NMR spectrum was 7.6 to 6.6 ppm, and the ³¹ P-NMR spectrum was 10 to 6, -11 to -14, and -16 to -21 ppm. And the weight average molecular weight measured by GPC was 1500 (polystyrene equivalent value).

The composition of this product was [N = P (OC ₆ H ₄ CN) _0.33 (OPH) _1.67 ] from the results of elemental analysis of carbon, hydrogen, nitrogen and phosphorus. It was confirmed that the target compound was synthesized according to the ratio. The product did not show a definite melting point and its decomposition temperature by TG / DTA analysis was 327 ° C.

Synthesis Examples 16 to 19
A phenoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15 except that the proportions of 4-cyanophenol and phenol used in Synthesis Example 15 were changed. Table 4 shows the results.

From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of these products and the measurement results of ¹ H-NMR and ³¹ P-NMR spectrum, the composition of the products matched the charge ratio of 4-cyanophenol and phenol, It was confirmed that the desired product was synthesized.

Synthesis Example 20
The phenol used in Synthesis Example 15 was changed to 4-isopropylphenol, and an isopropylphenoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15. Table 5 shows the results. From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of the product and the measurement results of ¹ H-NMR and ³¹ P-NMR spectrum, the composition of the product was determined to be the charging ratio of 4-cyanophenol and 4-isopropylphenol. It was confirmed that the target compound was synthesized.

Synthesis Example 21
The phenol used in Synthesis Example 15 was changed to 2-naphthol, and a naphthoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15. Table 5 shows the results. From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus and the results of ¹ H-NMR and ³¹ P-NMR spectroscopy of the product, the composition of the product was found to be one in proportion to the charging ratio of 4-cyanophenol and 2-naphthol. Therefore, it was confirmed that the desired product was synthesized.

Synthesis Example 22
A 4-cyanophenoxy group was prepared in the same manner as in Synthesis Example 15 except that phenol used in Synthesis Example 15 was changed to N-propanol and 4-cyanophenol was changed to 2-cyanophenol, and these sodium salts were prepared with sodium metal. A propoxyphosphazene compound having the following formula was synthesized. Table 5 shows the results. According to the elemental analysis results of carbon, hydrogen, nitrogen and phosphorus, and the ¹ H-NMR and ³¹ P-NMR spectra, the composition of these products matched the charging ratio of 2-cyanophenol and N-propanol, and the target compound was synthesized. I confirmed that it was done.

Synthesis Example 23
A phenol having a 4-cyanophenoxy group was prepared in the same manner as in Synthesis Example 15 except that the phenol used in Synthesis Example 15 was replaced with 2-ethylhexanol, and the sodium salt of 2-ethylhexanol and 4-cyanophenol was prepared with sodium metal. An ethylhexyloxyphosphazene compound was synthesized. Table 5 shows the results. From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of the product and the measurement results of ¹ H-NMR and ³¹ P-NMR spectrum, the composition of the product was determined to be the charging ratio of 4-cyanophenol and 2-ethylhexanol. It was confirmed that the target compound was synthesized.

Synthesis Example 24
2.20 mol of phenol used in Synthesis Example 15 was replaced with 2.00 mol of 2-allylphenol and 0.20 mol of N-propanol, and the sodium salt of 2-allylphenol, N-propanol and 4-cyanophenol was replaced with metallic sodium A phosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15 except for the preparation of the above. Table 5 shows the results. From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus and the results of ¹ H-NMR and ³¹ P-NMR spectroscopy, the composition of the product was found to be 4-cyanophenol, 2-allylphenol and N-propanol. It was confirmed that the target product was synthesized.

Synthesis Example 25
1.5 mol (521.6 g) of hexachlorocyclotriphosphazene was heated to 250 ° C. for 12 hours under a nitrogen atmosphere, and a dichlorophosphazene polymer was obtained by ring-opening polymerization. Unreacted hexachlorocyclotriphosphazene was removed by sublimation at 70 ° C. under reduced pressure for 7 hours. Chlorobenzene was added to 224.3 g (yield: 43%) of the obtained dichlorophosphazene polymer to prepare a 20% solution. In the same manner as in Synthesis Example 15, a toluene solution of cyanophenol and a sodium salt of phenol was prepared.

580 g of a 20% chlorobenzene solution in which 1 unit mol (115.9 g) of the dichlorophosphazene polymer prepared above was dissolved was added dropwise to the toluene solution of the sodium salt of phenols at an internal temperature of 30 ° C. or lower while stirring. The solution was refluxed for 12 hours. The reaction mixture was concentrated and reprecipitated in a 5% aqueous sodium hydroxide solution. Next, the precipitated polymer was dissolved in tetrahydrofuran and reprecipitated in water. This operation was performed three times. The produced polymer was vacuum-dried (vacuum drying conditions: 80 ° C., 5 mmHg, 12 hours) to obtain 213 g of a slightly yellow viscous liquid. Table 5 shows the results. From the elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of the product, and the measurement results of ¹ H-NMR and ³¹ P-NMR spectrum, the composition of the product matches the charge ratio of 4-cyanophenol and phenol, It was confirmed that the target compound was synthesized.

Examples 38 to 48
To a resin consisting of 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin, 15 parts of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Examples 15 to 25 are added, mixed with a mixer, and then melt-kneaded using a laboplast mill. Thus, a flame-retardant resin composition was obtained.

A test piece having a predetermined shape was prepared from this composition by a hot press, and a combustion test based on the UL-94 test method, and measurement of Izod impact strength and heat deformation temperature were performed according to the following methods. Table 6 shows the results.
-Combustion test It was performed according to the UL-94 specified vertical combustion test method and used as an index of flame retardancy. (Specimen: 1/16 inch thick, 5 inch long, 0.5 inch wide)
-Izod impact strength Measured at 23 ° C by a method based on JIS K-7110, and used as an index of impact resistance. (Test piece thickness 1/8 inch, with V notch)
Heat deformation temperature Measured at a load of 18.6 kg / cm ² by a method based on ASTM D-648, and used as an index of heat resistance.

Comparative Example 12
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 38, except that triphenyl phosphate was used in place of the phosphazene compound used in Example 38.

Comparative Example 13
A sample was prepared and evaluated in the same manner as in Example 38, except that a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used instead of the phosphazene compound used in Example 38. Table 6 shows the results.

Comparative Example 14
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 38, except that no flame retardant was added.

Example 49
A sample was prepared by adding 0.5 part of zinc chloride in the composition of Example 38, and the flame retardancy and the heat distortion temperature were evaluated. Table 6 shows the results.

Example 50
In the formulation of Example 38, 0.6 part of a commercially available polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., trade name: F-201) was added to prepare a sample, and evaluation of flame retardancy and heat distortion temperature was performed. went. Table 6 shows the results.

Examples 51 to 55
To a resin consisting of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene, 15 parts of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Examples 15 to 19 were added. After mixing with a mixer, the mixture was melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition. The combustion test based on the UL-94 test method, the measurement of the Izod impact strength and the measurement of the heat distortion temperature were performed according to the methods described above. Table 6 shows the results.

Comparative Example 15
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 51, except that triphenyl phosphate was used in place of the phosphazene compound used in Example 51.

Comparative Example 16
In place of the phosphazene compound used in Example 51, a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used, and sample preparation and evaluation were performed in the same manner as in Example 51. Table 6 shows the results.

Comparative Example 17
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 51 without adding the flame retardant.

Example 56
To 100 parts of nylon-6 having a number average molecular weight of 25,000, 10 parts of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 was added, mixed with a mixer, and then melt-kneaded using a laboplast mill. A flammable resin composition was obtained.

試 料 A sample piece was prepared in the same manner as in Example 38, and a combustion test based on the UL-94 test method, an Izod impact strength and a heat distortion temperature were measured. Table 6 shows the results.

Comparative Example 18
A sample was prepared and evaluated in the same manner as in Example 38 except that a condensed phosphoric acid diphenyl ester crosslinked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used instead of the phosphazene compound used in Example 56. Table 6 shows the results.

Example 57
After mixing 70 parts of a polycarbonate resin, 30 parts of a polybutylene terephthalate resin and 20 parts of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 with a mixer, the mixture is melt-kneaded using a Labo Plastmill to obtain a flame-retardant resin composition. Obtained.

試 料 A sample piece was prepared in the same manner as in Example 38, and a combustion test based on the UL-94 test method, an Izod impact strength and a heat distortion temperature were measured. Table 6 shows the results.

Comparative Example 19
A sample was prepared and evaluated in the same manner as in Example 57, except that the condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used instead of the phosphazene compound used in Example 57. Table 6 shows the results.

Example 58
A varnish was prepared by adding 10 parts of the phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 to 100 parts of a bisphenol-A type epoxy resin to prepare a varnish. . Subsequently, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or more to produce glass epoxy plates having a thickness of 1/8 and 1/16 inch, and cut into prescribed dimensions to obtain test pieces.

燃 焼 Using this test piece, a combustion test based on the UL-94 test method, and measurement of Izod impact strength and heat distortion temperature were performed in accordance with the above-described methods. Table 6 shows the results. No juicing was observed during hot pressing.

Example 59
A sample was prepared and evaluated in the same manner as in Example 58, except that the compound synthesized in Synthesis Example 23 was used instead of the phosphazene compound having a cyanophenoxy group (the compound synthesized in Synthesis Example 15) used in Example 58. Table 6 shows the results. No juicing was observed during hot pressing.

Comparative Example 20
In place of the phosphazene compound synthesized in Synthesis Example 15, a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used, and sample preparation and evaluation were performed in the same manner as in Example 58. Table 6 shows the results. Juicing was observed during hot pressing.

Comparative Example 21
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 58, except that no flame retardant was added.

From Table 6, it can be seen that the resin composition of the present invention has excellent balance of excellent flame retardancy, impact resistance and heat resistance by optimizing and blending each resin and phosphazene ( Examples 38-59). Further, in Example 49, by adding a small amount of zinc chloride to a mixed resin of an aromatic polycarbonate resin, an ABS resin and a phosphazene compound having a cyanophenoxy group, more excellent flame retardancy and impact resistance were exhibited. I understand. On the other hand, when a phosphate ester compound is used as the flame retardant, the flame retardancy and heat resistance are poor, and the practical utility value is low (Comparative Examples 12 to 13, 15 to 16, and 18 to 20).

Example 60
A resin composition comprising 75 parts of an aromatic polycarbonate resin (trade name: Iupilon S-2000N, manufactured by Mitsubishi Engineering-Plastics Corporation) and 25 parts of ABS resin (trade name: Santac UT-61, manufactured by Mitsui Chemicals, Inc.) 100 parts, 5.0 parts of triphenyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.), 5.0 parts of fexophosphazene synthesized in Synthesis Example 14, and polytetrafluoroethylene (trade name: G-307, Asahi Glass Co., Ltd.) 0.6 parts were kneaded with a twin-screw extruder and pelletized to produce pellets of the flame-retardant resin composition of the present invention.

Comparative Examples 22 and 23
In Example 60, it carried out similarly to Example 60 except not using a triphenyl phosphate and a phenoxy phosphazene together, and using only 10 parts of a triphenyl phosphate (Comparative Example 22) or only 10 parts of a phenoxy phosphazene (Comparative Example 23). Thus, pellets of the resin composition were produced.

Examples 61 to 63
In Example 60, instead of triphenyl phosphate as a halogen-free organic phosphorus compound, triphenylphosphine oxide (manufactured by Kanto Kagaku Co., Ltd., Example 61), tricresyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd., Example 62) ) Or resorcinol bis (2,6-dimethylphenyl phosphate) (Example 63), except that pellets of the flame-retardant resin composition of the present invention were produced in the same manner as in Example 60.

Comparative Examples 24-26
In Examples 61 to 63, only a triphenylphosphine oxide (Comparative Example 24), only tricresyl phosphate (Comparative Example 25) or resorcinol bis (2,6-dimethyl) was used without using a halogen-free organic phosphorus compound and phenoxyphosphazene. Pellets of the resin composition were produced in the same manner as in Examples 61 to 63, except that 10 parts of phenyl phosphate) (Comparative Example 26) was used.

Example 64
Pellets of the flame-retardant resin composition of the present invention were produced in the same manner as in Example 60 except that the phosphazene compound synthesized in Synthesis Example 3 was used instead of phenoxyphosphazene.

Example 65
Example 60 A pellet of the flame-retardant resin composition of the present invention was produced in the same manner as in Example 60 except that the phosphazene compound synthesized in Synthesis Example 4 was used instead of phenoxyphosphazene.

Example 66
The present invention was carried out in the same manner as in Example 60, except that a modified PPE resin (trade name: Xylon X9108, manufactured by Asahi Kasei Kogyo Co., Ltd.) was used in place of the mixed resin of the polycarbonate resin and the ABS resin. Of the flame-retardant resin composition of Example 1.

樹脂 The resins, halogen-free organic phosphorus compounds and phosphazene compounds in Examples 60 to 66 and Comparative Examples 22 to 26 are shown in Table 7 below. The amount in parentheses is the amount (parts).

PC: aromatic polycarbonate resin (trade name: Iupilon S-2000N, manufactured by Mitsubishi Engineering-Plastics Corporation)
ABS: ABS resin (trade name: Santac UT-61, manufactured by Mitsui Chemicals, Inc.)
TPP: triphenyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.)
TPPO: triphenylphosphine oxide (manufactured by Kanto Chemical Co., Ltd.)
TCP: tricresyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.)
LBDP: resorcinol bis (2,6-dimethylphenyl phosphate)
Pellets of the resin compositions obtained in Examples 60 to 66 and Comparative Examples 22 to 26 were injection-formed to prepare test pieces of a predetermined shape, and a combustion test based on a UL-94 test method, a flexural modulus, The heat distortion temperature, Izod impact strength and melt flow rate were measured. The combustion test, the measurement of the heat distortion temperature and the measurement of the Izod impact strength were performed according to the methods described above. The measurement of the flexural modulus and the melt flow rate was performed according to the method shown below.
-Flexural modulus Measured by a method according to JIS-K7203.
-Melt flow rate Measured by applying a load of 10 kg at 240 ° C by a method based on JIS-K7210.

These results are shown in Table 8 below.

Example 67
100 parts of bisphenol-A type epoxy resin (trade name: EP5400, manufactured by Asahi Denka Kogyo KK), 7.5 parts of triphenyl phosphate, 7.5 parts of phenoxyphosphazene synthesized in Synthesis Example 14, and polytetrafluoroethylene (G -307) 0.6 part was mixed to produce a varnish of the flame-retardant resin composition of the present invention.

The varnish was impregnated into a glass cloth and then dried to obtain a prepreg. Five prepregs were stacked and pressed at 160 ° C. at 50 kg / cm ² to produce a 1.6 mm thick glass epoxy plate. A test piece was prepared by cutting to a size of 12.7 cm and a width of 1.3 cm. This test piece was subjected to each of the tests described above. Table 8 shows the results.

Claims (4)

General formula (1)

[Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ]
A cyclic phosphazene compound represented by the general formula (2):

[Where X represents a group -N = P (OPh) ₃ or -N = P (O) OPh, and Y represents a group -P (OPh) ₄ or a group -P (O) (OPh) ₂ . n shows the integer of 3-1000. Ph is the same as above. ]
A flame retardant comprising at least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula: (4) A flame-retardant resin composition obtained by blending 0.1 to 100 parts by weight of the flame retardant according to claim 1 and 0.01 to 50 parts by weight of an inorganic filler with respect to 100 parts by weight of a thermoplastic resin or a thermosetting resin. Flame retardancy obtained by blending 0.1 to 50 parts by weight of the flame retardant of claim 1 and 0.1 to 50 parts by weight of a halogen-free organic phosphorus compound with respect to 100 parts by weight of a thermoplastic resin or a thermosetting resin. Resin composition. (4) A flame-retardant resin molded article obtainable by molding the flame-retardant resin composition according to (2) or (3).