WO2005087852A1 - Reactive flame retardant and flame-retardant processed resin obtained with the same - Google Patents

Abstract

A reactive flame retardant which imparts excellent flame retardancy to resins even when added in a small amount and can be prevented from bleeding out; and a flame-retardant processed resin obtained with the flame retardant. The reactive flame retardant is, for example, an organophosphorus compound represented by the following general formula (I) wherein R1 to R5 have at least one unsaturated group at an end. The flame-retardant processed resin is obtained by solidifying a resin composition containing this organophosphorus compound and then reacting the compound by heating or irradiation with a radiation.

Description

 Reactive flame retardant and flame-retardant resin processed product using the same

 The present invention relates to, for example, a flame retardant used for a resin molded product and the like, and a flame-retardant resin processed product using the same, and more particularly, to a halogen-free non-halogen flame retardant.

 Light

 Fine 1

 Background art

 Thermoplastic resins such as polyester and polyamide, and thermosetting resins such as epoxy have excellent moldability, mechanical strength, and electrical properties as general-purpose resins and engineering plastics. It is widely used in various fields. Products such as resin molded products are required to be flame-retardant from the viewpoint of safety for the purpose of preventing fires due to high temperatures.For example, standards such as UL 94 have been established as flame-retardant grades. Has been.

 In general, it is known that the addition of a halogen substance is effective in making such a resin material flame-retardant, and is used by adding it to a resin. The mechanism of the halogen-based flame retardant is that the halogenated radicals are mainly generated by thermal decomposition, and the halogenated radicals capture the organic radicals as the combustion source, thereby stopping the chain reaction of combustion. It is said to exhibit flammability.

 However, flame retardants containing a large amount of halogen compounds may generate dioxins depending on the combustion conditions, and in recent years there has been an increasing demand for reducing the amount of halogens from the viewpoint of reducing the burden on the environment. Therefore, various non-halogen flame retardants containing no halogen compound have been studied.

As such non-halogen flame retardants, inorganic flame retardants such as metal hydrates and red phosphorus, and organic phosphorus flame retardants such as phosphate esters have been studied, but aluminum hydroxide and magnesium hydroxide have been studied. In the case of hydrated metal hydrate, 'the effect of imparting flame retardancy is not so high, so it is necessary to incorporate a large amount into the resin. Therefore, the moldability of the resin deteriorates, and the mechanical strength of the obtained molded product tends to decrease. Is limited. Red phosphorus has a high flame-retardant effect, but impairs electrical properties due to poor dispersion, generates dangerous gases, reduces formability, and easily causes bleeding.

 On the other hand, as a phosphorus-based flame retardant such as a phosphate ester, for example, JP-A-2002-20394 discloses a piperazine salt of an acidic phosphate ester having a phosphorinane structure or a C1-6 alkylenediamine salt. It is disclosed for use as a flame retardant.

 Japanese Patent Application Laid-Open No. 2002-80633 discloses a flame retardant for resins containing a salt composed of an aromatic phosphate such as monophenyl phosphate and monotolyl phosphate and an aliphatic amine such as piperazine as main components. It has been disclosed.

 Furthermore, Japanese Patent Application Laid-Open No. 2002-138096 discloses that a halogen-free flame-retardant formulation exhibits excellent flame-retardant effects, as well as excellent heat resistance and water resistance properties of molded articles, and is used in electric laminates. It is disclosed that a phosphorus-containing phenol compound is used as a flame retardant for obtaining a flame-retardant epoxy resin having excellent adhesion.

 Furthermore, Japanese Patent Application Laid-Open No. 5-331179 discloses an organic cyclic phosphorus compound having a bifunctional hydroxyl group, which is particularly useful as a stabilizer for a polymer compound and a flame retardant.

 However, the phosphoric ester compounds used in JP-A-2002-20394, JP-A-2002-80633, and JP-A-2002-138096 described above have poor flame retardancy. It was necessary to mix at a high concentration because it was sufficient.

 In addition, since there is no reactive group in the molecule to react with the resin component, the flame retardant component easily migrates in the resin, volatilizes during molding and contaminates the mold, There is a problem that the flame retardant bleeds out. For this reason, the thermal, mechanical, and electrical properties of the resin processed product were reduced.

Further, the organic cyclic phosphorus compound disclosed in Japanese Patent Application Laid-Open No. 5-331179 functions as a reactive flame retardant in a resin having a reactive group capable of binding to a hydroxyl group, such as an epoxy resin. However, for example, a resin that does not have a reactive group capable of bonding to a hydroxyl group, such as a normal olefin resin, cannot form a crosslink, so that the flame retardant component easily migrates through the resin and volatilizes during molding. Dirty mold There were problems such as dyeing and bleeding out of the flame retardant on the resin surface.

 Therefore, an object of the present invention is to provide excellent flame retardancy and heat resistance even when a small amount is added to a resin, and to prevent bleed-out of a flame retardant, etc. In addition, mechanical properties, electrical properties, dimensional stability, An object of the present invention is to provide a reactive flame retardant excellent in moldability and a flame-retardant resin processed product using the same. Disclosure of the invention

 That is, the reactive flame retardant of the present invention is a reactive flame retardant having reactivity with a resin, and imparting flame retardancy by binding to the resin by the reaction. ) Or (Π), characterized by containing an organic phosphorus compound having an unsaturated group at the terminal.

… ( _Π )

(In formula (I) or (Π), each molecule contains at least one PC bond, and 結合 ι ^ and Ar ₂ are each a bifunctional aromatic containing 20 or less carbon atoms and free of mobile hydrogen.) Represents a hydrocarbon group, and n is an integer of 0 to 2. Ri R ⁵ is one NHC H ₂ CH = CH ₂ , one N (CH ₂ CH = CH ₂ ) ₂ , —〇CH ₂ CH = CH ₂ , — CH ₂ CH = CH ₂ , —CH ₂ CH ₂ OCH = CH ₂ , one (C ₆ H ₄ ) —CH = CH ₂ , —〇 (C ₆ H ₄ ) one CH = CH ₂ , _CH ₂ (C ₆ H ₄ ) _CH = CH ₂ , —NH (C ₆ H ₄ ) —CH = CH ₂ , N (CH ₂ CH = CH ₂ ) — (C ₆ H ₄ ) —CH = CH ₂ , O—R—〇OC — C (R,) = CH _2. , —NH—R—NHCO—C (R ′) = CH ₂ , or an aryl group having 12 or less carbon atoms. R represents an alkylene group having 2 to 5 carbon atoms, R ′ represents hydrogen or a methyl group, and at least one of Ri R ⁵ is a CH = CH ₂ group or —C (CH ₃ ) Including two CH ₂ groups. )

 According to the reactive flame retardant of the present invention, since an organic phosphorus compound having at least one terminal unsaturated bond in one molecule is used, the terminal unsaturated bond is bonded to the resin by heat or radiation. To react. As a result, the flame retardant component is stably present in the resin, so that the pre-out of the flame retardant can be prevented, and the flame retardancy can be imparted for a long time even by adding a small amount.

 Further, since one molecule contains two or more phosphorus atoms, the phosphorus content is high. In addition, since it contains a PC bond that is easily dissociated, it is easy to generate P radicals with high flame retardant effect. Therefore, flame retardancy can be improved.

 Further, since it contains a bifunctional aromatic hydrocarbon group containing no labile hydrogen having 20 or less carbon atoms, the molecular weight is increased and the energy is stabilized. As a result, the thermal decomposition temperature is improved, so that kneading to the resin, vaporization of the flame retardant during molding, and decomposition of the flame retardant due to heat and shear during molding can be prevented, thereby improving moldability. In addition, since a large amount of carbon is contained, soot is generated and deposited when the resin is decomposed, so that the flame retardancy is improved.

 On the other hand, the flame-retardant resin processed product of the present invention comprises, after solidifying a resin composition containing the above-described reactive flame retardant and a resin, heating and irradiating the resin with the resin and the reactive flame retardant. A flame-retardant resin processed product obtained by the reaction, wherein the reactive flame retardant is contained in an amount of 1 to 20% by mass based on the entire flame-retardant resin processed product.

 According to the flame-retardant resin processed product of the present invention, the terminal unsaturated bond of the organic phosphorus compound is reacted with the resin by heating or irradiation with radiation, so that the flame retardant component is stably present in the resin. . This prevents the bleed-out of the flame retardant and improves the flame retardancy effect. Therefore, even if the addition amount of the reactive flame retardant to the entire flame-retardant resin processed product is as small as 1 to 20% by mass. The flame retardancy can be given for a long time.

 In addition, since the resin is cross-linked into a three-dimensional network structure by the combination of the flame retardant and the resin, the resulting resin processed product has chemical stability, heat resistance, mechanical properties, electrical properties, dimensional stability, and flame retardancy. It is possible to obtain a resin molded product excellent in all of the properties and moldability, and it is possible to particularly improve heat resistance and mechanical strength. Further, thin-wall molding can be performed.

In the flame-retardant resin processed product, the resin composition preferably contains two or more types of the reactive flame retardants, and at least one type is the polyfunctional reactive flame retardant. Good.

 According to this aspect, the reaction rate required for crosslinking can be controlled by the combined use of flame retardants having different reactivities, so that it is possible to prevent the resin from shrinking due to rapid progress of the crosslinking reaction. In addition, the inclusion of a polyfunctional flame retardant forms a uniform three-dimensional network structure of the above-mentioned organic phosphorus compound, so that heat resistance and flame retardancy are improved and more stable resin properties are obtained. .

 In the above-described processed flame-retardant resin product, the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant has at least one unsaturated group at a terminal. It is preferably a cyclic nitrogen-containing compound.

 According to this embodiment, even with a cyclic nitrogen-containing compound having at least one unsaturated group at the terminal, the resin can be cross-linked into a three-dimensional network structure by bonding the flame retardant and the resin. While reducing costs, it is possible to obtain resin molded products that are excellent in chemical stability, heat resistance, mechanical properties, electrical properties, dimensional stability, flame retardancy, and moldability of the resulting resin processed products. In addition, since it contains nitrogen, the compatibility with the resin is further improved particularly when a polyamide resin is used as the resin.

 In the above-mentioned processed flame-retardant resin product, the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant is an addition-type flame retardant having no reactivity. It is preferred that there be. By using a non-reactive additive flame retardant such as phosphate ester, melamine, metal hydroxide, silicon, etc. in combination with the above reactive flame retardant, the reactive flame retardant alone due to a synergistic effect The flame retardancy can be further improved as compared with the case (1), and the cost of the flame retardant can be reduced.

 Further, in the above-mentioned flame-retardant resin processed product, the resin composition further contains a cross-linking agent having no flame retardancy but having reactivity with the resin, and the cross-linking agent is mainly It is preferably a polyfunctional monomer or oligomer having an unsaturated group at the terminal of the skeleton. Also in this embodiment, the resin can be cross-linked into a three-dimensional network structure by bonding the cross-linking agent and the resin, so that the obtained resin processed product has chemical stability, heat resistance, mechanical properties, electrical properties, dimensional stability, A resin molded article having excellent flame retardancy and excellent moldability can be obtained. .

Moreover, in the above-mentioned flame-retardant resin processed product, it is preferable to contain 1 to 35% by mass of the inorganic filler with respect to the whole of the flame-retardant resin processed product. Above all, the inorganic filling It is preferable that the composition contains a layered clay in which a silicate layer is laminated as an agent, and the layered clay is contained in an amount of 1 to 10% by mass based on the entire flame-retardant resin processed product. According to this aspect, it is possible to obtain a resin processed product excellent in dimensional stability by suppressing shrinkage and decomposition due to crosslinking. In addition, when a layered clay formed by laminating a silicate layer is included as an inorganic filler, a nano-ordered layered clay is dispersed in the resin to form a hybrid structure with the resin. . This improves the heat resistance, mechanical strength, and the like of the obtained flame-retardant resin processed product.

 Furthermore, in the above-mentioned flame-retardant resin processed product,

It is preferable to contain 5 to 40% by mass of reinforcing fibers. According to this aspect, by including the reinforcing fiber, it is possible to improve the mechanical strength of the resin processed product such as tension, compression, bending, impact, and the like, and it is possible to prevent a decrease in physical properties with respect to moisture and temperature. . Further, in the above-mentioned processed flame-retardant resin product, it is preferable that the resin and the reactive flame retardant are obtained by reacting by irradiation with an electron beam or a beam of a dose of 10 kGy or more. According to this aspect, after the resin is solidified by molding or the like, it can be bridged by radiation, so that a resin processed product can be manufactured with high productivity. By setting the dose within the above range, it is possible to prevent uneven formation of a three-dimensional network structure due to insufficient dose, and to prevent predation due to unreacted crosslinker residue. In particular, when the irradiation dose is set to 10 to 45 kGy, deformation and shrinkage due to internal distortion of a resin processed product due to oxidative decomposition products generated by excessive dose can be prevented.

 Further, in the above-mentioned flame-retardant resin processed product, it is also preferable that the resin and the reactive flame retardant are obtained by reacting at a temperature 5 ° C. or more higher than the temperature at which the resin composition is molded. . According to this aspect, a radiation irradiating device or the like is not required, and it can be suitably used particularly in a resin composition containing a thermosetting resin.

 Further, in the above-mentioned flame-retardant resin processed product, it is preferable that the flame-retardant resin processed product is one selected from a molded product, a coating film, and a sealant. The flame-retardant resin processed product of the present invention has excellent flame retardancy as described above and can prevent pre-out, so that it can be applied not only to ordinary resin molded products but also to coatings as coating agents and the like. It is also suitably used as a sealant for semiconductors and liquid crystal materials.

Further, in the above-mentioned flame-retardant resin processed product, it is preferable that the flame-retardant resin processed product is used as an electric component or an electronic component. The flame-retardant resin of the present invention As described above, heat-resistant products have excellent heat resistance, mechanical properties, electrical properties, dimensional stability, flame retardancy, and moldability. It is particularly preferably used as a part. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. First, the reactive flame retardant of the present invention will be described.

 The reactive flame retardant of the present invention is a reactive flame retardant having reactivity with a resin, and imparting flame retardancy by binding to the resin by the reaction, and has the following general formula (I) or Is characterized by being an organic phosphorus compound represented by (で).

R 'R ³ R ⁴

 P-Ar P-Ar ― p

 … (Π)

R ^{2 n} R ⁵

(In the formula (I) or (Π), each molecule contains at least one PC bond, and Ar and Ar ₂ are each a bifunctional compound containing 20 or less carbon atoms and no mobile hydrogen.) Represents an aromatic hydrocarbon group, and n is an integer of 0 to 2. Also, R ¹ ! ^ ⁵ is — NHCH ₂ CH = CH ₂ , 1 N (CH ₂ CH = CH ₂ ) ₂ , One CH ₂ CH = CH ₂ , —CH ₂ CH = CH ₂ , One CH ₂ CH ₂ OCH = CH ₂ , — (C ₆ H ₄ )-CH = CH ₂ , — 0 (C ₆ H ₄ ) -CH = CH ₂ , -CH ₂ (C ₆ H ₄ ) -CH = CH ₂ , -NH (C ₆ H ₄ ) -CH-CH ₂ , N (CH ₂ CH = CH ₂ ) — (C ₆ H ₄ ) — CH = CH ₂ , 110 R — O〇 C-C (R ') 2 CH ₂ , -NH-R-NHCO-C (R') = CH ₂ , or aryl having 12 or less carbon atoms Wherein R is an alkylene group having 2 to 5 carbon atoms, R, represents a hydrogen or a methyl group, and at least one of 尺¹ to! ^ ⁵ is 1 "1 = (: 11 ₂ group or - (((including 11 ₃₎ = CH ₂ groups). Among the above organic phosphorus compounds, the general formula (I) is a compound having a pentavalent phosphorus, and the general formula (は) is a compound having a trivalent phosphorus.

The above organic phosphorus compound has at least one terminal unsaturated bond, —CH = CH ₂ group or —C (CH ₃ ) 2 CH ₂ group. Here, —CH = CH ₂ group or 1 C (CH ₃ ) = CH ₂ group is a functional group for bonding to a resin by heating or irradiation with radiation or the like described below. It is preferable that two or more —CH 2 CH ₂ groups or 1 C (CH ₃ ) = CH ₂ groups be present in one molecule.

Examples of aryl groups having 12 or less carbon atoms include, for example, one C ₆ H ₅ (phenyl group), —C ₆ H ₅ 〇H (hydroxyphenyl group), one C ₆ H ₅ —C ₆ H ₅ OH (hydroxy group Biphenyl group), —a-C ₁₀ H ₇ (hy-naphthyl group), 1_C ₁₀ H ₇ (j3-naphthyl group) and the like.

A r A r ₂ represents a bifunctional aromatic hydrocarbon group containing no mobile hydrogen having 20 or less carbon atoms, and n is an integer of 0 to 2. Here, the mobile hydrogen is easily formed with a hydrogen bond such as -0H (hydroxyl group), -NHC0- (amide bond), -NHC00- (urethane bond), and so forth. It is a highly reactive hydrogen contained in the functional group that easily reacts with room temperature at room temperature to generate hydrogen.

In the present invention, the bifunctional aromatic hydrocarbon group refers to, for example, a bifunctional aromatic group such as a 1,4-phenylene group PP-C ₆ H ₄ —pC ₆ H ₄ —. not only hydrocarbon groups, such as the above-mentioned hydroxy Hue alkenyl group Ya one _{P- C 6 H 4 - S 0} 2 - p_C 6 H 4 - like, further oxygen or sulfur, etc. in addition to the aromatic hydrocarbon group It is meant to include a group containing a hetero atom. If at least one PC bond is contained in one molecule, each Ar or Ar ₂ is one p—C ₆ H ₄ —O—, —〇 one p—C ₆ H ₄ — 0 It may contain a P-O bond such as-. When n is 2, each Ar ₂ may be the same or different.

Examples of such Ar Ar ₂ include —p-C ₆ H ₄ —, one p-C ₆ H ₄ —O—, —〇—p-C ₆ H ₄ —O—, — p_C ₆ H _{4 - pC 6 H 4 -, _p-} C 6 H 4 - CH 2 - pC 6 H 4 -, -pC 6 H 4 -C (CH 3) 2 - pC 6 H 4 -, i_C 6 H 4 - C (= _{〇) 1 - C 6 H 4 -} , .- p- C 6 H 4 - S0 2 - p- C 6 H 4 _, 2, 6- C 10 H 6 wards (2, 6-Nafuchire emission group) And the like.

In the general formula (I) or (Π), the content of phosphorus in one molecule is 6 to 20. It is preferable that the _W t%.

 Specific examples of the organic phosphorus compound represented by the general formula (I) include compounds represented by the following structural formulas (1-1) to (1-23). Of these, (I-1 1) to (1-12) are examples in which n is zero, that is, when there are two phosphorus atoms in one molecule, and (I-1 13 to (1-20) 1, that is, an example in which there are three phosphorus atoms in one molecule, and (1-21)-(1-23) are examples in which n force is 2, that is, when there are four phosphorus atoms in one molecule It is.

(1-1)

(1-2)

(1-3)

() Iwl

(1-9)

(1-11)

(I-1 12)

(1-14)

(I-1 15)

(1-19)

(1-22)

(1-23) Further, specific examples of the organophosphorus compound represented by the above general formula (が) include compounds represented by the following structural formulas (Π-1) to (Π-23). this house,

(Π-1) to (H-12) are examples where n is zero, that is, when there are two phosphorus atoms in one molecule, and (H-13 to (Π-20), where n is 1, that is, 1 This is an example where the number of phosphorus atoms in the molecule is three, and (H_21) to (Π−23) are examples where n is 2, that is, four phosphorus atoms in one molecule.

(Π-8)

(Π— 11)

(Π-12)

(Π -13)

(Π-14)

(Π-15)

(Π-16)

222 CC〇HCCOOCHHH =

222C0 CHHHCH〇〇OC =

(Π -22)

(Π-23) As described above, the compound of the general formula (I) or (Π) has a ridge type in which phosphorus atoms on both sides are bonded via Ar 1 or Ar 2, that is, a PC bond. It has the structure of Further, at least one of the groups attached to the phosphorus atom contains a terminal unsaturated bond.

In the synthesis of the above compound, for example, the compound (I-11) is obtained by reacting 4,4′-dichlorobiphenyl as a starting material, reacting it with phosphorus oxychloride, and further reacting it with aryl bromide. It can be synthesized by introducing an unsaturated group into the terminal. Further, for example, the compound (Π-1) is prepared by reacting 4,4′-dichlorobiphenyl as a starting material, reacting it with phosphorus trichloride, and further reacting it with aryl bromide to obtain an unterminated compound. It can be synthesized by introducing a saturated group.

Then, instead of aryl bromide, for example, allylamine, allylic alcohol, diarylamine, or the like is used. In the above general formula (I) or (Π),! ^ ¹ ~! ^ ⁵ can be changed. In addition, more specific synthesis examples, such as the case where n is 1 or 2 in the formula (I) or (H), will be described in Examples described later.

 Next, a flame-retardant resin processed product using the reactive flame retardant will be described.

 The flame-retardant resin processed product of the present invention is obtained by solidifying a resin composition containing a resin and an organic phosphorus compound represented by the above general formula (I) or (H), and then subjecting the resin composition to heating or irradiation of radiation. Thus, it is obtained by reacting the resin with the reactive flame retardant, and contains the reactive flame retardant in an amount of 1 to 20% by mass based on the entire resin composition.

 First, as the resin used in the present invention, any of a thermoplastic resin and a thermosetting resin can be used and is not particularly limited.

 Examples of the thermoplastic resin include a polyamide resin, a polybutylene terephthalate resin, a polyester resin such as polyethylene terephthalate, a polyacrylic resin, a polyimide resin, a polycarbonate resin, Polyurethane resin, polystyrene, acrylonitrile-styrene copolymer, polystyrene resin such as acrylonitrile-butadiene styrene copolymer, polyacetal resin, polyolefin resin, polyphenylene oxide resin, polyphenylene sulfide resin, polybutylene resin And the like. Above all, use of polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate resin, polyacrylic resin, polyacetyl resin, polyphenylene oxide resin, from the viewpoint of mechanical properties and heat resistance Is preferred.

Examples of the thermosetting resin include epoxy resin, resin resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, alkyd resin, and silicone resin. Among them, it is preferable to use an epoxy resin, a phenol resin, an unsaturated polyester resin, and a urea resin from the viewpoint of mechanical properties and heat resistance. The content of the reactive flame retardant is preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, based on the entire resin composition. No. If the content of the reactive flame retardant is less than 1% by mass, the crosslinking by the reaction is insufficient, and the mechanical, thermal, and electrical properties of the obtained resin processed product are not favorable. %, The amount of the reactive flame retardant becomes excessive, unreacted monomers and decomposed gas of the reactive flame retardant are generated, and the oligomerized product bleeds out, and the mechanical properties of the resin processed product Is undesirably reduced.

 Among the organophosphorus compounds represented by the above general formula (I) or (Π), in the present invention, two or more kinds of compounds having different reactivities, that is, different numbers of the above functional groups in one molecule are used. It is preferable to use two or more compounds in combination. This makes it possible to control the reaction rate required for crosslinking, thereby preventing the resin composition from shrinking due to rapid progress of the crosslinking reaction.

 Further, among the organic phosphorus compounds represented by the above general formula (I) or (II), it is preferable to contain at least a polyfunctional reactive flame retardant. Thereby, a uniform three-dimensional network structure is formed by the organic phosphorus compound.

 Further, in the present invention, an addition-type flame retardant having no reactivity other than the reactive flame retardant may be further contained. As such a flame retardant, a non-halogen flame retardant is preferable, and metal hydrates represented by aluminum hydroxide and magnesium hydroxide, and monophosphoric acids such as triphenyl phosphate and tricresyl phosphate are preferred. Esters, bisphenol A bis (diphenyl) phosphate, resorcinol bis

Examples thereof include condensed phosphoric acid esters such as (diphenyl) phosphate, ammonium polyphosphate, polyphosphoramide, red phosphorus, guanidine phosphate, etc., derivatives of cyanuric acid or isocyanuric acid, melamine derivatives, and silicon-based flame retardants.

These flame retardants may be used alone or in combination of two or more. The content of the flame retardant other than the reactive flame retardant is 1 to 20 mass% of the flame retardant other than the reactive flame retardant with respect to the entire resin composition in order to prevent bleeding and deterioration of mechanical properties. %, More preferably 3 to 15% by mass. Also, as a flame retardant having a reactivity other than the reactive flame retardant with respect to 1 part by mass of the reactive flame retardant, It is more preferable to contain 0.5 to 10 parts by mass of a cyclic nitrogen-containing compound having at least one unsaturated group at a terminal. Specific examples of the group having an unsaturated group at the terminal include diacrylate, dimethacrylate, diarylate, triacrylate, trimethacrylate, triarylate, tetraacrylate, tetramethacrylate, tetraarylate, and the like. However, from the viewpoint of reactivity, acrylates such as diacrylate, triacrylate, and tetraacrylate are more preferable.

 Further, examples of the cyclic nitrogen-containing compound include an isocyanuric ring and a cyanuric ring.

 Specific examples of the cyclic nitrogen-containing compound having at least one unsaturated group at the terminal include the above-mentioned derivatives of sialic acid or isocyanuric acid, for example, isocyanuric acid E〇modified diacrylate, isocyanuric acid Examples thereof include EO-modified triacrylate and triisocyanuryl triacrylate.

 Further, in the present invention, a crosslinking agent which does not have flame retardancy but has reactivity with the resin may be further contained. As such a crosslinking agent, a polyfunctional monomer or oligomer having an unsaturated group at the terminal of the main skeleton can be used.

 In the present invention, the cross-linking agent having no flame retardancy but having reactivity with the resin means a cross-linking agent (reactivity) having no cross-linking property (reactivity). Excludes reactive flame retardants that have both crosslinkability and flame retardance, such as cyclic nitrogen-containing compounds having at least one unsaturated group at the terminal.

Examples of such a cross-linking agent include di- to tetra-functional compounds represented by the following general formulas (a) to (c). Here, X is a main skeleton, R ^{6 to} R ⁹ are functional groups having an unsaturated group at the terminal, (a) is a bifunctional compound, (b) is a trifunctional compound, and (c) ) Is a tetrafunctional compound.

RXR ⁷ (a)

R ⁸

^Ri "X—R ⁷ … ( _b) R ⁸

RXR ⁷ (c)

R ⁹

Specifically, in the following general formula, the main skeleton X is an aliphatic alkyl such as glycerin or a pennin erythritol derivative, or a trimellit, pyromellit, tetrahydrofuran, or a trimethylenetrioxane. Examples of the structure include an aromatic ring and bisphenol.

 (a-1)

(b-1) (b-2)

(b-3) (b— 4)

(c-1) (c-2) Specific examples of the above-mentioned cross-linking agents include, as bifunctional monomers or oligomers, bisphenol FE-modified diacrylate, bisphenol A-EO-modified diacrylate, and trifunctional monomer or oligomer. Diacrylates such as propylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, and pentaerythritol diacrylate monostearate; and dimethacrylates and diarylates thereof.

 Examples of the trifunctional monomer or oligomer include triacrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane PO-modified triacrylate, and trimethylolpropane EO-modified triacrylate. Of trimethacrylate and triarylate.

 Examples of the tetrafunctional monomer or oligomer include ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and the like. The above crosslinking agents are used as the main skeleton X: trimellitic acid, pyromellitic acid, tetrahydrofurantetracarboxylic acid, 1, 3, 5 — trihydroxybenzene, glycerin, pentaeristol, 2, 4, 6 — Tris (chloromethyl) — 1, 3, 5 — trioxane, etc., one of which is a functional group having an unsaturated group at the terminal, acrylyl bromide, aryl alcohol, arylamine, methallyl bromide , Methallyl alcohol, methallylamine and the like.

 The crosslinking agent is preferably contained in an amount of 0.5 to 10 parts by mass based on 1 part by mass of the reactive flame retardant.

The resin composition used in the present invention may contain an inorganic filler, a reinforcing fiber, various additives, and the like, in addition to the resin and the flame retardant. By containing an inorganic filler, the mechanical strength of the resin processed product can be improved and the dimensional stability can be improved. In addition, it serves as a substrate on which the reactive flame retardant is adsorbed, so that the reactive flame retardant is uniformly dispersed.

 As the inorganic filler, conventionally known ones can be used, and typical ones are metal powders such as copper, iron, nickel, zinc, tin, stainless steel, aluminum, gold, and silver, fumed silica, Aluminum silicate, calcium silicate, silicic acid, hydrated calcium silicate, hydrated aluminum silicate, glass beads, power pump rack, quartz; ^ powder, mica, talc, my power, clay, titanium oxide, iron oxide, zinc oxide, carbonate Examples include calcium, magnesium carbonate, magnesium oxide, calcium oxide, magnesium sulfate, potassium titanate, and diatomaceous earth. These fillers may be used alone or in combination of two or more, or may be those treated with a known surface treatment agent. The content of the inorganic filler is preferably from 1 to 35% by mass, more preferably from 1 to 20% by mass, based on the whole flame-retardant resin product. If the content is less than 1% by mass, the mechanical strength of the flame-retardant resin processed product is insufficient, the dimensional stability is insufficient, and the adsorption of the reactive flame retardant is insufficient. On the other hand, if it exceeds 35% by mass, the flame-retardant resin processed product becomes brittle, which is not preferable.

 Among the above-mentioned inorganic fillers, it is particularly preferable to use a layered clay obtained by laminating a silicate layer. The layered clay formed by stacking the silicide layers is a clay having a structure in which a silicide layer having a thickness of about Inm and a length of one side of about 100 nm is stacked. Therefore, the layered clay is dispersed in the resin on the order of nanometers to form a hybrid structure with the resin, thereby improving the heat resistance, mechanical strength, and the like of the obtained flame-retardant resin processed product. The average particle size of the layered clay is preferably 100 nm or less.

 Examples of the layered clay include montmorillonite, force olinate, and my strength, and montmorillonite is preferred from the viewpoint of excellent dispersibility. Further, the layered clay may be surface-treated in order to improve the dispersibility in the resin. As such a layered clay, commercially available ones may be used, such as “Nanomer” (trade name, manufactured by Nissho Iwai Bentonite Co., Ltd.) and “Somasif” (trade name, manufactured by Corpo Chemical Co., Ltd.). Can be used.

The content of the layered clay is preferably 1 to 10% by mass based on the entire flame-retardant resin processed product. That's right. The layered clay may be used alone or in combination with another inorganic filler.

 In addition, by containing the reinforcing fibers, for example, in the case of a molded product, the mechanical strength is improved and the dimensional stability can be improved. Examples of the reinforcing fiber include glass fiber, carbon fiber, and metal fiber, and it is preferable to use glass fiber from the viewpoint of strength and adhesion to a resin or an inorganic filler. These reinforcing fibers may be used alone or in combination of two or more kinds, or may be treated with a known surface treatment agent such as a silane coupling agent.

 Further, it is preferable that the glass fiber is surface-treated and further coated with a resin. Thereby, the adhesiveness with the thermoplastic polymer can be further improved. As the surface treatment agent, a known silane coupling agent can be used. Specifically, at least one alkoxy group selected from the group consisting of a methoxy group and an ethoxy group, an amino group, a vinyl group, Examples thereof include a silane coupling agent having at least one reactive functional group selected from the group consisting of an acrylic group, a methacryl group, an epoxy group, a mercapto group, a halogen atom, and an isocyanate group.

 The coating resin is not particularly limited, and examples thereof include a urethane resin and an epoxy resin.

 The compounding amount of the reinforcing fiber is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, based on the whole flame-retardant resin product. If the content is less than 5% by mass, the mechanical strength of the flame-retardant resin processed product is reduced, and the dimensional stability is insufficient. It is not desirable because processing becomes difficult.

 • It contains the above-mentioned inorganic filler and reinforced fiber, and preferably contains 65% by mass or less of the inorganic filler and reinforced fiber with respect to the entire flame-retardant resin product, and 55% by mass or less. More preferably, it is contained. When the content of the inorganic filler and the reinforcing fiber exceeds 65% by mass, the ratio of the resin component is reduced, and the moldability is lowered, and the obtained resin processed product becomes brittle and the physical properties are deteriorated. Absent.

The resin composition used in the present invention includes various commonly used components other than those described above, such as crystal nuclei, as long as the physical properties such as heat resistance, weather resistance, and impact resistance of the present invention are not significantly impaired. Agents, colorants, antioxidants, release agents, plasticizers, heat stabilizers, lubricants, UV inhibitors And other additives. As will be described later, for example, when a resin is reacted with a reactive flame retardant by ultraviolet rays, an ultraviolet initiator or the like can be used.

 The colorant is not particularly limited, but is preferably one that does not fade by irradiation as described below.For example, inorganic pigments such as red iron black, carbon black, graphite, and metal complexes such as phthalocyanine are preferably used. Can be

 The flame-retardant resin processed product of the present invention is obtained by solidifying the above-mentioned resin composition, and then reacting the resin with the reactive flame retardant by heating or irradiation with radiation.

 Conventionally known methods are used for solidification of the resin composition.For example, in the case of a resin composition containing a thermoplastic resin, the thermoplastic resin and the reactive flame retardant are melt-kneaded and pelletized, and then the conventional method is used. It can be formed by known injection molding, extrusion molding, vacuum molding, inflation molding or the like. Melt kneading can be carried out using a conventional melt kneading machine such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. The kneading temperature can be appropriately selected depending on the type of the thermoplastic resin.For example, in the case of a polyamide resin, the kneading is preferably performed at 240 to 280 ° C., and the molding conditions can also be set as appropriate. Not limited. Since no cross-linking has progressed at this stage, the extra spool part during molding can be recycled as a thermoplastic resin.

 On the other hand, in the case of a thermosetting resin, similarly to the above, after the thermosetting resin and the reactive flame retardant are melt-kneaded and pelletized, for example, conventionally known injection molding, compression molding, transfer molding, and the like. It can be formed by using such as.

 When forming a coating film, the resin composition may be applied as it is, or may be appropriately diluted with a solvent or the like to form a solution or suspension that can be applied, and then dried and formed into a film by a conventionally known method. May be. As a method for forming a coating film, a coating method such as roller one-coating, spraying, dipping, and spin coating can be used, and is not particularly limited.

 In the above resin composition, the unsaturated bond at the terminal of the reactive flame retardant reacts with the resin and undergoes a crosslinking reaction by heating or irradiation with radiation, and is stably present in the resin.

When heating is used as a means for reacting the reactive flame retardant with the resin, the reaction temperature is preferably at least 5 ° C higher than the resin molding temperature, more preferably at least 10 ° C higher. Is more preferable. When radiation is used as a means for cross-linking, an electron beam, a ray, an a ray, an X ray, an ultraviolet ray, or the like can be used. The radiation in the present invention means radiation in a broad sense, and specifically includes not only particle beams such as electron beams and α-rays but also electromagnetic waves such as X-rays and ultraviolet rays.

 Of the above, electron beam or r-beam irradiation is preferred. For the electron beam irradiation, a known electron accelerator or the like can be used, and the acceleration energy is preferably 2.5 MeV or more. Irradiation using a known cobalt 60 radiation source or the like can be used for the irradiation with the alpha rays. Irradiation using a known cobalt 60 radiation source or the like can be used for the irradiation with the alpha rays. r-rays are preferable because they have a higher transmittance than electron beams, so that irradiation is uniform and preferable. However, since the irradiation intensity is high, dose control is necessary to prevent excessive irradiation.

 The irradiation dose of radiation is preferably 10 kGy or more, more preferably 10 to 45 kGy. Within this range, a crosslinked resin article having excellent physical properties can be obtained. If the irradiation dose is less than 10 kGy, the formation of a three-dimensional network structure due to cross-linking becomes non-uniform, and the unreacted cross-linking agent may be prematurely dropped. On the other hand, if it exceeds 45 kGy, internal distortion of the resin-processed product due to the oxidative decomposition product remains, which is not preferable because deformation or shrinkage occurs.

 The flame-retardant resin processed product of the present invention obtained as described above has, as a molded product, excellent mechanical properties, electrical properties, dimensional stability, and moldability in addition to heat resistance and flame retardancy. Therefore, electrical or electronic parts that require high heat resistance and flame retardancy, as well as automobile parts and optical parts, such as members for supporting contacts such as electromagnetic switches and breakers, printed circuit boards, etc. It can be suitably used as a substrate, a package for an integrated circuit, a housing for electric components, and the like.

 -Specific examples of such electrical or electronic components include power receiving boards, switchboards, electromagnetic switches, circuit breakers, transformers, electromagnetic contactors, circuit protectors, relays, transformers, various sensors, and various types of motors. , A diode, a transistor, and a semiconductor device such as an integrated circuit.

 It can also be suitably used as interior parts such as cooling fans, bumpers, brake covers and panels, sliding parts, sensors, and automobile parts such as motors.

Further, it can be used as a flame-retardant coating film on not only molded articles but also the above-mentioned molded articles and fibers. Further, when used as sealing, coating, insulating, etc. of the above-mentioned electronic components or electric components such as semiconductor devices, excellent heat resistance and flame retardancy can be imparted. That is, for example, the above-described resin composition is sealed to cure the resin, and the above-described reaction by heating or irradiation is performed to seal electronic components and electric elements such as semiconductor chips and ceramic capacitors. It can be used as a flame retardant sealant. As a sealing method, sealing by injection molding, potting, transfer molding, injection molding, compression molding or the like is possible. The electronic components and electrical components to be sealed are not particularly limited, but include, for example, liquid crystals, integrated circuits, transistors, thyristors, diodes, capacitors, and the like.

 As described above, according to the present invention, a non-halogen-based reactive flame retardant which is excellent in flame retardancy even when added in a small amount to a resin and can prevent bleed-out and the like, and flame retardancy using the same A resin processed product can be provided. Therefore, this flame-retardant resin processed product can be suitably used for resin molded products such as electric parts and electronic parts, sealing agents for semiconductors and the like, and coating films. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.

 [Synthesis of reactive flame retardant of general formula (I)]

 Synthesis Example 1 (Synthesis of Compound (I-I-1))

 In a 500 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, put 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF vigorously. A solution of 23.1 g (0.100 mol) of 4,4'-dichlorobiphenyl in 200 ml of distilled THF was added dropwise with stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

Put 91.99 g (0.600 mol) of phosphorus oxychloride and 30 mL of distilled THF into a 1 000m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel. The mixture was stirred while gently flowing nitrogen, and the whole amount of the organolithium compound solution was added at 0 to 5 ° C over 3 hours from a dropping funnel. 6 at the same temperature The reaction was allowed to proceed for 12 hours at room temperature, and the solvent and excess phosphorus oxychloride were distilled off under reduced pressure. 300 ml of dry ethyl acetate was added to the residue and mixed, and the remaining salt was removed by filtration. The solution was distilled off under reduced pressure to prepare 4,4'-bis (dichlorophosphoryl) biphenyl.

 In a 1 000 m 1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 21.87 g (0.900 mol) of metal magnesium pieces and 200 ml of distilled getyl ether were placed. A solution of 72.59 g (0.600 mol) of acrylyl bromide in 300 ml of distilled getyl ether was added dropwise with vigorous stirring, and a gentle reflux of boiling point was maintained by the heat of reaction. After the addition was completed in about 3 hours, the mixture was refluxed at the boiling point for 1 hour. After cooling, excess magnesium metal was removed by decantation to prepare a magnesium bromide solution.

 The total amount of the above 4,4′-bis (dichlorophosphoryl) biphenyl and distilled THF 30 Om1 were charged into the same reactor as above, and the entire amount of the above arylmagnesium bromide solution was added at 0 to 5 ° C. from a dropping funnel. Added over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and getyl ether was distilled off under reduced pressure. The residue was poured into 1,000 ml of water while adding an acid so that the pH was maintained near neutrality, and extracted five times with 100 ml of ethyl acetate. After washing with water, the ethyl acetate phase was separated, dried over anhydrous sodium sulfate, the desiccant was removed by filtration, and the solution was distilled off under reduced pressure to obtain 38.58 g (yield 94%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1-1) described above.

 Infrared absorption spectrum (cm-R: V ring 1605, 1495, ri OC 1635, ri P = 1160-1250

TOF-Mass spectrum (M / Z): 412,413 (Calculated molecular weight = 410.4328)

Negation R scan Bae spectrum _{(δ, ppm): CH 2} = 4.6~4.7 (8H), = CH_ 5.5~5.6 (4H), -CH 2 - 3.3 (8H), ' aromatic CH 6.8 to 7.4 (8H )

 Synthesis Example 2 (Synthesis of Compound (I-I-2))

 Instead of the aryl magnesium bromide solution of Synthesis Example 1, aryl alcohol 34.8

The same procedure as in Synthesis Example 1 was repeated except that a solution of 4 g (0.600 mol) and 60.71 g (0.600 mol) of triethylamine in THF30Om1 was used.

54 g. (96% yield) was obtained.

The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1_2) described above. Infrared absorption spectrum (cm- ¹ ): V ring 1605, 1495, Li OC 1635, Li P = 01160-1250, vP-0-C 1220, 1260

 TOF-Mass spectrum (M / Z): 476,477 (Calculated molecular weight = 474.4328)

Negation R scan Bae spectrum _{(d, ppm): CH 2} = 5 · 0~5.1 (8H), = CH - 5 · 8~5.9 (4Η), -CH 2 - 3.3 (8Η), aromatic CH 6.8 to 7.4 (8H)

 Synthesis Example 3 (Synthesis of Compound (I-13))

 Instead of the allylic magnesium bromide solution in Synthesis Example 1, 58.30 g (0.600 mol) of diarylamine and 60.71 g (0.600 mol) of triethylamine in THF 300 m1 Except for using the solution, 65.55 g (96% yield) of the target compound was obtained in the same manner as in Synthesis Example 1.

 The measurements of the compound in the infrared absorption spectrum, T-F_Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-13) described above.

Infrared absorption spectrum (cm- ¹ ): V ring 1603, 1495, v C = C 1635, P = 01160-1250 TOF-Mass spectrum (M / Z): 632, 633 (calculated molecular weight = 630.7508)

NMR spectrum (δ, ppm): CH ₂ = 4.9 ~ 5.0 (16H), = CH_ 5.8 ~ 5.9 (8H), _CH ₂ _ 3.K16H), aromatic CH 6.8 ~ 7.4 (8H)

 Synthesis Example 4 (Synthesis of Compound (I-14))

 Instead of the aryl magnesium bromide solution of Synthesis Example 1, a solution of 34.25 g (0.600 mol) of arylamine and 60.71 (0.600 mol) of triethylamine in 300 ml of THF was used. Except for the above, 45.17 g (yield: 96%) of the target compound was obtained in the same manner as in Synthesis Example 1.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-14) described above.

Infrared absorption spectrum (cm- ¹ ): Re NH 3260, δΝΗ 1630, Le ring 1603, 1495, Le C = C 1635, vP = 1160-1250

 TOF-Mass spectrum (M / Z): 472, 473 (Calculated molecular weight = 470.4924)

NMR scan Bae spectrum (<5, ppm): CH 2 = 4.7~4.8 (8H), = CH- 5.5~5.7 (4H), -CH 2 - 2.8 (8H),> NH 3.3 (4H), aromatic C -H 6.8-7.4 (8H)

 Synthesis Example 5 (Synthesis of Compound (I-I-5))

1000m equipped with reflux tube with drying tube, mechanical stirrer, nitrogen inlet tube, dropping funnel 1 In a four-necked flask, add 21.87 g (0.900 mol) of metal magnesium pieces and 200 ml of distilled getyl ether, and stir vigorously to give 2-chloroethylvinyl ether 63.93 g (0.9%). 300 mol) of distilled getyl ether (300 mol) was added dropwise, and a gentle reflux of boiling point due to reaction heat was maintained. After the addition was completed in about 3 hours, the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal magnesium was removed by decantation to prepare a vinyloxyxetil magnesium chloride solution.

 Thereafter, the desired compound was prepared in the same manner as in Synthesis Example 1 except that the total amount of the vinyloxyxetyl magnesium chloride solution described above was used instead of the aryl magnesium bromide solution of Synthesis Example 1. g (yield 92%) was obtained.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1-5) described above.

Infrared absorption spectrum (cm- ¹ ): Les ring 1603, 1495, Les C = C 1635, Les P = 01160-1250, V C-0-C 1060

 TOF-Mass spectrum (M / Z): 532, 533 (Calculated molecular weight = 530.5400)

Thigh R scan Bae spectrum _{(δ, ppm): CH 2} = 5.1~5.2 (8H), = CH- 6 · 2~6.3 (4H), -0CH 2 - 3.2 (8H) -CH 2 P- 2.7 (4H) , Aromatic C-H 6.8 ~ 7.4 (8H)

 Synthesis Example 6 (Synthesis of Compound (I-I-6))

 In a 50 Om 1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF were placed. A solution of 23.91 g (0.100 mol) of bis (4-chlorophenyl) ether in distilled THF 20 Om1 was added dropwise with vigorous stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

In a 1000m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, put 91.99 g (0.600 mol) of phosphorus oxychloride and 300 ml of distilled THF into the flask and gently add The mixture was stirred while flowing nitrogen, and the entire amount of the above-mentioned organolithium compound solution was added from 0 to 5 t from a dropping funnel over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phosphorus oxychloride were distilled off under reduced pressure. Add 30 Oml of dry ethyl acetate to the residue and stir to remove residual salt and filter out the solution. The pressure was distilled off to prepare bis (4-dichlorophosphorylphenyl) ether.

 In a 1000m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.187 g (0.900 mol) of magnesium metal pieces and distilled Jetil ether 2 Add 0 Oml and add vigorously stirring -promostyrene 1 O 9.87 g (0.600 mol) of distilled getyl ether 30 Om 1 solution dropwise to maintain a gentle boiling point reflux due to reaction heat. Was. After the addition was completed in about 3 hours, the mixture was refluxed for another 1 hour. After cooling, excess metal magnesium was removed by decantation to prepare a styrylmagnesium bromide solution.

 Thereafter, 62.07 g (yield) of the target compound was obtained in the same manner as in Synthesis Example 1 using the entire amount of the above bis (4-dichlorophosphorylphenyl) ether and the entire amount of the p-styrylmagnesium bromide solution. Rate 92%).

 The measurements of the compound in the infrared absorption spectrum, T-F-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-16) described above.

Infrared absorption spectrum (cnf ¹ ): Les ring 1605, 1495, vC = C 1630, Les P = 01160-1250 TOF-Mass spectrum (M / Z): 676, 677 (Calculated molecular weight = 674.7160)

R spectrum (δ, ppm): CH ₂ = 4.6 to 4.7 (8H), = CH- 6.2 to 6.3 (4H), aromatic CH 6.8 to 7.4 (24Η)

 Synthesis Example 7 (Synthesis of Compound (I-I-7)) ''

 In a 50 Om 1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF were placed. And add viscous bis (4-chlorophenyl) methane 23.7 1 g (0.

(100 mol) of a distilled THF 20 Om 1 solution was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

 100 Om equipped with reflux tube with drying tube, mechanical stirrer, nitrogen inlet tube, dropping funnel

1 In a four-necked flask, add phenylphosphoryl dichloride (1.169) g (0.600 mol) and distilled THF (30 Om1), stir while gently flowing nitrogen, and mix at 0-5 ° C. , The entire amount of the organolithium compound solution was added from the dropping port over 3 hours. The reaction is carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phenylphosphoryl The chloride was distilled off under reduced pressure. 30 Oml of dry ethyl acetate was added to the residue and the mixture was stirred, the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure to prepare bis [4- (chlorophenylphosphoryl) phenyl] methane.

 A 100-m 4-neck flask equipped with a reflux tube with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel; 36.5 g (0.300 mol) of J-hydroxystyrene, triethylamine 30.36 g (0.300 mol) and THF200 ml were added, and at 0 to 5 ° C., the above-mentioned total amount of bis [4- (chlorophenylphosphoryl) phenyl] methane was THF 30 Om 1. The solution was added dropwise. After reacting at the same temperature for 3 hours and at room temperature for 10 hours, about half of the solvent was distilled off under reduced pressure, poured into 1500 ml of water, and extracted with 150 ml of ethyl acetate five times.The ethyl acetate phase was sulfuric anhydride. Drying over sodium, filtration and evaporation under reduced pressure gave 60.70 g (yield 93%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1-7) described above.

 Infrared absorption spectrum (cm-ray: y ring 1605, 1495, v C = C 1630, P = 01160-1250, v P-O-C 1220, 1260

 TOF-Mass spectrum (M / Z): 654, 655 (calculated molecular weight = 652.6672)

Thigh R spectrum (δ, ppm): CH ₂ = 4.5 to 4.7 (4H), = CH- 6.2 to 6.3 (2H), phenyl -CH ₂ -phenyl 2.8 (2H), aromatic CH 6.8 to 7.4 (26Η) )

 Synthesis Example 8 (Synthesis of Compound (I-18))

 In a 500 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.3000 mol) of lithium metal pieces and 100 ml of distilled THF were placed. Then, while vigorously stirring, a solution of 2.97 g (0.100 mol) of 2,2-bis (4-chlorophenyl) propane in 200 ml of distilled THF was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

A 100-m 1-neck flask equipped with a reflux tube with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was charged with 147.02 g (0.600 mol) of α-naphthyl phosphoryl dichloride and distilled THF 30 Om Add 1 and stir while gently flowing nitrogen.Add all the above organolithium compound solution from 0 to 5 ° C over 3 hours from dropping funnel. Yeah. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess α_naphthylphosphoryl dichloride were distilled off under reduced pressure. 300 ml of dry ethyl acetate is added to the residue and stirred, the remaining salt is removed by filtration, and the solution is distilled off under reduced pressure to give 2,2-bis [4- (chloro-naphthylphosphoryl) phenyl] propane. It was adjusted.

 A 100.000m four-necked flask equipped with a reflux tube with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was charged with 3.75 g (0.3000 mol) of aminostyrene and 30.36 of triethylamine. g (0.300 mol) and 200 ml of THF, and at 0-5 ° C., a solution of the above total amount of 2,2-bis [4- (chloro-naphthylphosphoryl) phenyl] propane in THF 30 Om 1 Was dropped. After reacting at the same temperature for 3 hours and then at room temperature for 10 hours, about half of the solvent was distilled off under reduced pressure, poured into 1500 ml of water, extracted five times with 150 ml of ethyl acetate, and the ethyl acetate phase was extracted. After drying over anhydrous sodium sulfate, filtration and evaporation under reduced pressure, 73.99 g (yield 95%) of the desired compound was obtained.

 The measurements of the compound in the infrared absorption spectrum, T-F-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-18) described above.

Infrared absorption spectrum (cnf ¹ ): v H 3240, δ NH 1640, v ring 1605, 1495, C = C 1630, vP = 1160-1250

 TOF-Mass spectrum (M / Z): 780, 781 (Calculated molecular weight = 778.8702)

NMR spectrum (<5, ppm): CH ₂ = 4.5 to 4.7 (4Η), = CH- 6.1 to 6.2 (2Η),> NH 3.2 (2H), -CH ₃ 1. (6H), aromatic Tribe C_H 6.8 ~ 7.4 (30H)

 Synthesis Example 9 (Synthesis of Compound (I-19))

 16-2.65 g (0.600 mol) of -biphenylphosphoryl dichloride in place of para-naphthylphosphoryl dichloride and 47.77 g of N-aryl-aminostyrene in place of -aminostyrene Except for using 300 mol), 82.91 g (yield 91%) of the desired target compound was obtained in the same manner as in Synthesis Example 8.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-19) described above.

Infrared absorption spectrum (cnf ¹ ): V ring 1605, 1495, v C = C 1630, P = 0 = 1160-1250 T0F_Mass spectrum (M / Z): 913, 914 (calculated molecular weight = 911.075)

Awakening: R spectrum _{(δ, ppm): CH 2} = 4.4~4.5 and 4.7~4 · 8 (8Η), -CH- 5.7~5.8 and _{6.1~6.2 (4H), -CH 2 -} 2.8 (4H), -CH ₃ 1.4 (6H), Aromatic C-H6.7-7.6 (34Η) Synthesis Example 10 (Synthesis of Compound (I-I-10))

 Phosphoryl chloride was replaced by 80.99 g (0.600 mole) of phenylphosphoryl dichloride, and 47.9 g (0.3000 mole) of chloromethylstyrene was replaced by arylmethyl bromide. Except for the use, in the same manner as in Synthesis Example 1, 58.39 g (yield 92%) of the desired compound was obtained.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-10) described above.

Infrared absorption spectrum (cnr ¹ ): ring 1605, 1495, v C = C 1635, P = 0 1160-1250 TOF-Mass spectrum (M / Z): 636, 637 (calculated molecular weight = 634.6940)

Negation R scan Bae spectrum _{(δ, ppm): CH 2} = 4.7~4.8 (4H), = CH_ 5.5~5.6 (2H), -CH 2 - 3.4 (4H), aromatic CH 6.8 to 7.4 (26H)

 Synthesis Example 1 1 (Synthesis of Compound (I-111))

 A 100-m flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was charged with 2.08 g (0.300 mol) of lithium metal pieces and distilled THF 100 m. Then, a solution of 32.32 g (0.100 mol) of 4,4'-dichloro-1,1, -binaphthyl in 500 ml of distilled THF was added dropwise with vigorous stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation, and the solvent was concentrated under reduced pressure to about twice the concentration. After this, 69.67 g (0.600 mol) of 2-hydroxyethyl acrylate and 60.71 g (0.6000 mol) of triethylamine are used instead of the allylmagnesium bromide solution. In the same manner as in Synthesis Example 1 except that a THF 30 Om 1 solution of THF was used, 73.41 g (yield 91%) of the desired compound — was obtained.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-11) described above.

Infrared absorption spectrum (cm- ¹ ): Li 001720, ring 1605, 1500, Li OC 1635, v P = 1160-1250, v COC 1060

 TOF-Mass spectrum (M / Z): 808,809 (Calculated molecular weight = 806.7036)

NMR spectrum _{(δ, ppm): CH 2} = 5.3~5.4 (8H), = CH - 6.3~6.5 (4H), -COOCH 2 CH 2 - 3.3~3..6 (16H), aromatic CH 6.8 ~ 7.7 (12H) Synthesis Example 12 (Synthesis of Compound (I-I2))

 4,4′-bis (chlorophenylphosphoryl) biphenyl was prepared in the same manner as in Synthesis Example 1 except that phenylphosphoryl dichloride (1.169 g, 0.600 mol) was used instead of phosphorus oxychloride.

 N_ (2-aminoethyl) methacrylamide 38.45 g (0.300 mol) and triethylamine 30.36 g in a 1000 m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel (0.300 mol) of THF (400 ml) was added, and a 0,5 t solution of the above 4,4'-bis (chlorophenylphosphoryl) biphenyl in a THF (400 ml) solution was added dropwise over 4 hours. The reaction was carried out at the same temperature for 4 hours and at room temperature for 12 hours. About half of the solvent was distilled off under reduced pressure, poured into 200 Om 1 of water, and extracted five times with 150 mL of ethyl acetate. The ethyl acetate phase was dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain 60.23 g (yield: 92%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-12) described above.

Infrared absorption spectrum (cm— ¹ ): NH 3260, 3080, amide-Π 1645, ring 1605, 1495, VC = C 1630, vP = 1160-1250

 TOF-Mass spectrum (M / Z): 656, 657 (Calculated molecular weight = 654.6876)

Thigh R spectrum _{(δ, ppra): CH 2} = 4 · 7~5.0 (4Η), - CH 2 - 2.8~3.4 (8H),> NH 3, 1,3.5 (4H), -CH 3 1.6 (6H), aromatic CH 6.8-7.4 (18H)

 Synthesis Example 13 (Synthesis of Compound (I-I-3))

In a 1000m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 4.16 g (0.600 mol) of lithium metal pieces and 200 ml of distilled THF were added. With vigorous stirring, a solution of 44.62 g (0.200 mol) of 4,4'-dichlorobiphenyl in 40 mL of distilled THF was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation. To this solution was added a solution of 19.50 g (0.100 mol) of phenylphosphoryl dichloride in distilled THF 30 Om1 at 0-5 ° C over 3 hours from the dropping funnel with vigorous stirring. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and concentrated under reduced pressure to about 500 ml. In a 1000 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, put a solution of 91.99 g (0.600 mol) of phosphorus oxychloride in 200 ml of THF. At 55 ° C., the above concentrated solution was added from a dropping funnel over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phosphorus oxychloride were distilled off under reduced pressure. 300 ml of dry ethyl acetate was added to the residue and stirred, and the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure. The residue was converted into a 500 ml THF solution, reacted with an allylmagnesium bromide solution in the same manner as in Synthesis Example 1, and treated in the same manner to obtain 58.37 g of the desired compound (yield: 85%).

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-13) described above.

Infrared absorption spectrum (cm- ¹ ): V ring 1605, 1495, C = C 1635, v P = 0 1160-1250 TOF-Mass spectrum (M / Z): 688, 689 (calculated molecular weight = 686.7073)

丽R scan Bae spectrum _{(, ppm): CH 2 =} 4.6~4.7 (8H), = CH - 5.4~5.6 (4H), - CH 2 - 3.0 (8Η), aromatic CH 6.6~7 · 8 (21Η)

 Synthesis Example 14 (Synthesis of Compound (I-20))

 Distillation of 23.04 g (0.100 mol) of phenylphosphonyl dichloride in 30 000 m 1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was added. While stirring and cooling to 0-5 ° C while distilling 35.72 g (0.200 mol) of 5-chloro-1-mononaphthol and 25.30 g (0.250 mol) of triethylamine in THF The 30 Om1 solution was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and then at room temperature for 12 hours. Triethylamine hydrochloride was filtered off and evaporated to dryness under reduced pressure to obtain phenylphosphonylbis (5-kuguchi-1--1-naphthoxide) quantitatively. .

'' 400 mL of distilled THF as a whole was placed in a 1000 mL four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel.

5.0 g of metal magnesium strip was added and reacted at room temperature for 6 hours and at 40 ° C. for 6 hours to obtain phenylphosphonylbis (5-chloromagnesium-1-naphthoxide) quantitatively. . Excess magnesium metal was removed by decantation, and a solution of 9.99 g (0.600 mol) of phosphorus oxychloride in 200 ml of THF was added dropwise over 3 hours while cooling to -5 ° C. After reacting at the same temperature for 3 hours and at room temperature for 3 hours, the solvent and excess phosphorus oxychloride were distilled off under reduced pressure. The residue was made up as 50 Om 1 in THF and combined. It was reacted with an aryl magnesium bromide solution in the same manner as in Example 1 and treated in the same manner to obtain 62.44 g (yield 94%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TO F-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-120) described above.

Infrared absorption spectrum (cnf ¹ ): V ring 1603, 1495, v C = C 1635

 T0F-Mass spectrum (M / Z): 668, 669 (Calculated molecular weight = 666.6314)

Negation R scan Bae spectrum _{(δ, ρριη): CH 2} = 4.5~4.7 (8H), = CH- 5.3~5.6 (4Η), -CH 2 - 3.0 (8H), aromatic CH 6.6-7.8 (17H )

 Synthesis Example 15 (Synthesis of Compound (I-21))

 300 ml of aryloxyphosphoryl dichloride 52.48 g (0.300 mol) of distilled THF was placed in a 1 000 m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel. While stirring and cooling to 0-5 ° C, distillation of 1,5_ naphthyl diol diol 16.02 g (0.100 mol) and triethylamine 25.30 g (0.250 mol) THF 30 Om 1 The solution was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the triethylamine hydrochloride was filtered off and evaporated to dryness under reduced pressure to quantitatively obtain 1,5-bis (aryloxycyclophosphoric oxy) naphthalene. The whole amount was put in a 100 Oml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel as a solution of distilled THF40 Om1, stirred, and cooled to 0 to 5 ° C. A solution of 35.72 g (0.200 mol) of 5-chloro-1-1-naphthol and 25.30 g (0.2.50 mol) of triethylamine in distilled THF 30 Om1 was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the triethylamine hydrochloride was removed by filtration.

Cl-Np-0-P (= 0) (0CH ₂ CH = CH ₂ ) -Ο-Νρ-0-Ρ (= 0) (OCH ₂ CH = CH _z ) -0-Np-Cl (where Np is 1 , 5-naphthalene group) were obtained quantitatively.

The whole amount was put as a solution in distilled THF 40 Om1 into a 1,000 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, and stirred to obtain 5.0 g of metallic magnesium. And reacted at room temperature for 6 hours and at 40 for 6 hours.ClMg-Np.-0-P (= 0) (OCH ₂ CH = CH ₂ ) -0-Np-0-P (= 0) (OCH ₂ CH = CH ₂ ) -0-Np-MgCl (where Np is a 1,5-naphthalene group) was obtained quantitatively. Excess metal magnesium is removed by decantation, and while cooling to 0 to 5 ° C, 91.99 g of phosphorus oxychloride (0.600 Mol) in 200 ml of THF was added dropwise over 3 hours. 3 hours at the same temperature, at room temperature

After reacting for 3 hours, the solvent and excess oxychloride were distilled off under reduced pressure.

C 1 ₂ P (= 0) -Np-0-P (= 0) (OCH ₂ CH = CH ₂ ) -0-Np-OP (= 0) (0CH ₂ CH = CH ₂ ) -O-Np-P (= 0) (just Shi Np 1, 5-naphthoquinone evening alkylene group) C 1 ₂ to quantitatively obtain.

 The residue was stirred as a solution of 50 Oml in THF and cooled to 0-5 ° C with 34.85 g (0.600 mol) of aryl alcohol and 60.7 2 g of triethylamine (0.

(600 mol) in 20 Om 1 THF was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and triethylamine hydrochloride was removed by filtration and dried under reduced pressure to obtain 85.24 g (yield 94%) of the desired compound.

The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I-21) described above. , Infrared absorption spectrum (cm— ¹ ): Re ring '1606, 1500, C = C 1640

 TOF-Mass spectrum (M / Z): 974, 975 (Calculated molecular weight = 972.7976)

Awakening: R spectrum (<5, ppm): CH 2 = 4.4~4.7 (12H), = CH- 5.3~5.8 (6H), -CH 2 - 3.0

~ 3.2 (12H), aromatic C-H 6.6 ~ 7.8 (18H)

 Synthesis Example 16 (Synthesis of Compound (I-122))

 Distillation of 47.68 g (0.300 mol) of arylphosphonyl dichloride into a 100-m 4-neck flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping port Add 300 ml of THF, stir, and cool to 0-5 ° C. while cooling p-hydroquinone 11.01 g (0.100 mol) and triethylamine 25.30 g (0.25 mol). A 0 mol) distilled THF 30 Oml solution was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the toluenediamine hydrochloride was filtered off and evaporated to dryness under reduced pressure to obtain quantitatively 1,4-bis (arylcyclophosphonyloxy) benzene.

 The whole amount was put into a 100-Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel as a solution of 40 Oml of distilled THF, and stirred at 0 to 5 ° C. A solution of 34.2 g (0.200 mol) of 4-bromophenol and 25.30 g (0.250 mol) of triethylamine in THF 30 Om1 was added dropwise over 3 hours while cooling. did. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and triethylamine hydrochloride was removed by filtration.

Br- Φ -0-P (= 0) (CH ₂ CH = CH ₂ ) -0- -0-P (= 0) (CH ₂ CH = CH ₂ ) -0- φ -Br (where φ is 1, 4-f (Enylene group) was obtained quantitatively.

 The whole amount was put into a 100 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel as a 400 ml solution of distilled THF. Magnesium strips were added. Reaction for 6 hours at room temperature and 6 hours at 40 ° C,

BrMg- φ -0-P (= 0) (CH ₂ CH = CH ₂ ) -0- φ -0-Ρ (= 0) (CH ₂ CH = CH ₂ )-0_ φ-MgBr (where φ is 1, 4-phenylene group) was obtained quantitatively. Excess metallic magnesium was removed by decantation, and a solution of 9.99 g (0.600 mol) of phosphorus oxychloride in 200 ml of THF was added dropwise over 3 hours while cooling to 0 to 5 ° C. After reacting at the same temperature for 3 hours and at room temperature for 3 hours, the solvent and excess phosphorus oxychloride were distilled off under reduced pressure.01 ₂ Ρ-φ-0-Ρ (= 0) (CH ₂ CH = CH ₂ ) -O- -OP (= 0) (CH 2 CH = CH 2) _0_ (i - is PC1 ₂ (except φ quantitatively obtain 1,4_ phenylene group).

 The residue was stirred as a 500 ml THF solution and cooled to 0-5 ° C. with 34.26 g (0.6000 mol) of arylamine and 0.67 g (0.600 mol) of triethylamine. A 20 OmI THF solution was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and triethylamine hydrochloride was removed by filtration and dried under reduced pressure to obtain 62.29 g (yield: 93%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1-22) described above.

 Infrared absorption spectrum (cm-R: V ring 1604, 1496, v C = C 1635

 TOF-Mass spectrum (M / Z): 732,733 (Calculated molecular weight = 730.6546)

NMR spectrum (δ, ppm): CH ₂ = 4.4 to 4.8 (12H), = CH- 5.1 to 5.7 (6Η), -CH ₂ -3.0-to 3.7 (12H), aromatic C_H 6.6 ~ 7.8 (12H)

 Synthesis Example 17 (Synthesis of Compound (I-23))

 In the same manner as in Synthesis Example 16

C1 ₂ P-φ-0_P (= 0) (CH ₂ CH = CH ₂ ) -0-φ-0-P (= 0) (CH ₂ CH = CH ₂ ) _0--PC1 ₂ (where φ is 1, 4-phenylene group) was obtained quantitatively. Then, instead of arylamine, a solution of 5.8.30 g (0.600 mol) of diarylamine and 60.72 g (0.600 mol) of triethylamine in 20 Om 1 THF was added dropwise over 3 hours. . The reaction was carried out at the same temperature for 6 hours and then at room temperature for 12 hours. Triethylamine hydrochloride was removed by filtration and dried under reduced pressure to obtain the desired compound. 79.54 g (yield 96%) was obtained.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (1-23) described above.

Infrared absorption spectrum (cm— ¹ ): ring 1605, 1495, v C = C 1635

 TOF-Mass spectrum (M / Z): 892, 893 (Calculated molecular weight = 890.9130)

Negation R spectrum _{(d, ppm): CH 2} = 4.3~4 · 7 (20H), = CH- 5.0~5.6 (10H), _CH 2 - 3.0

~ 3.8 (20H), Aromatic C-H 6.6 ~ 7.9 (12H)

 [Synthesis of reactive flame retardant of general formula (Π)]

 Synthesis Example 18 (Synthesis of Compound (Π—1))

 In a 50 Oml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF were placed. And 4,4'-dichlorobiphenyl 22.3 1 g (0.

200 mol) of distilled THF was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

 100 m equipped with a reflux tube with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a drip port

1 In a four-necked flask, put 82.39 g (0.600 mol) of phosphorus trichloride and 300 ml of distilled THF, stir while gently flowing nitrogen, and at 0-5 ° C, The entire amount of the organic lithium compound solution was added from the dropping funnel over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phosphorus trichloride were distilled off under reduced pressure. 300 m to residue

The dried ethyl acetate of 1 was added and stirred, the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure to prepare 4,4′-bis (dichlorophosphier) biphenyl.

 100 m equipped with a reflux tube with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel

1 In a four-necked flask, add 2.1.87 g (0.900 mol) of metal magnesium pieces and distilled getyl ether 20 Om 1 and, with vigorous stirring, 72.5 9 g of aryl bromide

(0.60 mol) of a distilled acetyl ether 30 Om1 solution was added dropwise, and a gentle boiling point reflux state due to reaction heat was maintained. After the addition was completed in about 3 hours, the mixture was refluxed at the boiling point for 1 hour. After cooling, excess magnesium metal was removed by decantation to prepare a magnesium bromide solution. The total amount of the above 4,4'-bis (dichlorophosphier) biphenyl and 300 ml of distilled THF were charged into the same reactor as above, and the above arylmagnesium bromide was heated at 0 to 5 ° C. The whole amount of the solution was added from a dropping funnel over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and getyl ether was distilled off under reduced pressure. The residue was poured into 100 ml of water while adding acid so that the pH was kept near neutral, and extracted five times with 100 ml of ethyl acetate. After washing with water, the ethyl acetate phase was separated, dried over anhydrous sodium sulfate, the desiccant was removed by filtration, and the solution was distilled off under reduced pressure to obtain 36.33 g of the desired compound (yield: 96%). .

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-1) described above.

Infrared absorption spectrum (cnf ¹ ): V ring 1605, 1495, v C = C 1635.

 TOF-Mass spectrum (M / Z): 380,381 (Calculated molecular weight = 378.4328)

Awakening: R scan Bae spectrum (5, ppm):. CH 2 = 4.3~4.5 (8H), = CH - 5.0~5.1 (4H), -CH 2 - 2.6 (8H), aromatic CH from 6.7 to 7 probability)

 Synthesis Example 1 9 (Synthesis of Compound (Π_2))

 Synthetic Example1.8 Instead of the aryl magnesium bromide solution, aryl alcohol 34.

84 g (0.600 mol) and 60.71 g (0.600 mol) of triethylamine

The desired compound was prepared in the same manner as in Synthesis Example 18 except that a THF 300 ml solution was used.

40.70 g (92% yield) was obtained.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-2) described above.

Infrared absorption spectrum (cm- ¹ ): Les ring 1605, 1495, Les OC 1635, vP-0-C 1220, 1260 TOF-Mass spectrum (M / Z): 444,445 (Calculated molecular weight = 442.4328)

Momosupe vector _{(δ, ppm): CH 2} = 4.7~4.9 (8H), = CH - 5.3~5.4 (4H), -CH 2 - 3.2 (8Η), aromatic C_H 6.8 to 7.6 (8H)

 Synthesis Example 20 (Synthesis of compound (Π-3))

Instead of the arylmagnesium bromide solution of Synthesis Example 18, 58.30 g (0.600 mol) of diarylamine and 60.71 g (0.600 mol) of triethylamine in THF 300 m Except that one solution was used, 56.888 g (yield 95%) of a target compound was obtained in the same manner as in Synthesis Example 18. The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (III-3) described above.

 Infrared absorption spectrum (cm-RI: ring 1603, 1495, v C = C 1635

 TOF-Mass spectrum (M / Z): 600,601 (Calculated molecular weight = 598.7508)

R spectrum (δ, ppm): CH ₂ = 4.5 to 4.7 (16H), = CH- 5.2 to 5.4 (8H), -CH 3.1 (16H), aromatic C_H 6.8 to 7.4 (8H)

 Synthesis Example 2 1 (Synthesis of Compound (1-4))

 Instead of the allylmagnesium bromide solution of Synthesis Example 18, the THF of aryamine 34.25 g (0.600 mol) and triethylamine 60.71 g (0.600 mol) was used. Except that the 300 ml solution was used, 39.90 g (yield 91%) of the desired compound was obtained in the same manner as in Synthesis Example 18.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (IV-4) described above.

Infrared absorption spectrum (ciif ¹ ): v H 3060, δ NH 1615, v ring 1605, 1495, v C = C 1635

 TOF-Mass spectrum (M / Z): 440, 441 (Calculated molecular weight = 438.4924)

Negation R scan Bae spectrum _{(δ, ppm): CH 2} = 4.4~4.6 (8H), = CH - 5.2~5.3 (4H), -CH 2 - 2.8 (8H),> NH 3.3 (4H), aromatic C -H 6.8-7.4 (8H)

 Synthesis Example 2 2 (Synthesis of Compound (Π-5))

 A 100-m 4-neck flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was charged with 2.187 g (0.9000 mol) of metal magnesium pieces and distilled 200 ml of 1 ter was added, and while stirring vigorously, a solution of 63.93 g (0.600 mol) of 2-chloroethyl vinyl ether in 300 ml of distilled getyl ether was added dropwise. A gentle boiling point reflux due to the heat of reaction was maintained. After the addition was completed in about 3 hours, the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal magnesium was removed by decantation to prepare a vinyloxyshethylmagnesium chloride solution.

 Thereafter, the target compound was obtained in the same manner as in Synthesis Example 18 except that the above-mentioned total amount of vinyloxyshethyl magnesium chloride solution was used instead of the allylmagnesium bromide solution of Synthesis Example 18. 7 g (92% yield) was obtained.

Infrared absorption spectrum, TOF-Mass spectrum, NMR measurement of this compound The results are as follows, and the structure of the above compound (H-5) was confirmed. Infrared absorption spectrum (cm-R: V ring 1603, 1495, Les OC 1635, v C-0-C 1060 T0F-Mass spectrum (M / Z): 500, 501 (Calculated molecular weight = 498.5400)

NMR spectrum _{(δ, ppm): CH 2} = 4.3~4.5 (8H), = CH- 5.8~6.0 (4Η), -0CH r 3.2 (8H), -CH Z P- 2.7 (4H), aromatic C- Η 6.8-7.6 (8Η)

 Synthesis Example 2 3 (Synthesis of Compound (Π-6))

 In a 50 Oml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal pieces and 100 mL of distilled THF were added. m 1 was added thereto, and a solution of 23.91 g (0.100 mol) of distilled THF 20 Om 1 of bis (4-chlorophenyl) ether was added dropwise with vigorous stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

 In a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 8.39 g (0.600 mol) of phosphorus trichloride and 300 ml of distilled THF were added. The mixture was stirred while gently flowing nitrogen, and the whole amount of the organic lithium compound solution was added at 0 to 5 ° C over 3 hours from a dropping funnel. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phosphorus trichloride were distilled off under reduced pressure. The residue was mixed with 300 ml of dry ethyl acetate and stirred, the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure to prepare bis (4-dichlorophosphinylphenyl) ether.

 A 100-m1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel was charged with 2.187 g (0.900 mol) of metal magnesium pieces and distilled getyl ether 200 ml was added, and while stirring vigorously, a solution of 109.87 g (0.600 mol) of distilled getyl ether 30 Om1 in p-bromostyrene was added dropwise to maintain a gentle reflux of boiling point due to reaction heat. Was. After the addition was completed in about 3 hours, the mixture was refluxed for another 1 hour. After cooling, excess magnesium metal was removed by decantation to prepare a -styrylmagnesium bromide solution.

Thereafter, 57.84 g (yield) of the target compound was obtained in the same manner as in Synthesis Example 18 using the total amount of bis (4-dichlorophosphinylphenyl) ether and the total amount of p-styrylmagnesium bromide solution. 90%). The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-6) described above.

Infrared absorption spectrum (cm— ¹ ): y ring 1605, 1495, v C = C 1630

 TOF-Mass spectrum (M / Z): 644, 645 (Calculated molecular weight = 642.7160)

丽 R spectrum (δ, ppm): CH ₂ = 4.5 to 4.6 (8H), = CH- 5.9 to 6.0 (4Η), aromatic C-H 6.8 to 7.4 (24Η)

 Synthesis Example 24 (Synthesis of compound (Π-7))

 In a 50 Om 1 four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF were placed. Under vigorous stirring, a solution of 27.1 g (0.100 mol) of bis (4-chlorophenyl) methane in 200 ml of distilled THF was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

 In a 100-Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 107.39 g (0.600 mol) of phenylphosphieric dichloride and 300 ml of distilled THF were placed. The mixture was stirred while gently flowing nitrogen, and the entire amount of the organolithium compound solution was added at 0 to 5 ° C over 3 hours from a dropping funnel. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phenylphosphinyl dichloride were distilled off under reduced pressure. 300 ml of dry ethyl acetate was added to the residue and the mixture was stirred, the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure to prepare bis [4- (chlorophenylphosphinyl) phenyl] methane.

• In a 100 Om four-necked flask equipped with a reflux tube with a drying tube, mechanical stirrer, nitrogen inlet tube, and dropping funnel, 36.05 g (0.300 mol) of hydroxystyrene, 30.36 g of triethylamine ( 0.3 mol) and 200 ml of THF, and a solution of bis [4- (chlorophenylphosphinyl) phenyl] methane described above in THF30Om1 was added dropwise at 0 to 5 ° C. After reacting at the same temperature for 3 hours and then at room temperature for 10 hours, about half of the solvent was distilled off under reduced pressure, poured into 1500 ml of water, extracted with 150 ml of ethyl acetate five times, and the ethyl acetate phase was dried with anhydrous sodium sulfate. Drying, filtration and evaporation under reduced pressure gave 60.70 g (yield 93%) of the desired compound. The measurements of the compound in the infrared absorption spectrum, TOF_Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-7) described above.

Infrared absorption spectrum (cm- ¹ ): V ring 1605, 1495, v C = C 1630, y POC 1220, 1260 TOF-Mass spectrum (M / Z): 622, 623 (Calculated molecular weight = 620.6672)

Marauder R spectrum (δ, ppm): CH ₂ = 4.4 ~ 4.6 (4Η), = CH- 5.9 ~ 6.1 (2Η), phenyl -CH factory phenyl 2.8 (2H), aromatic C-H 6.8 ~ 7.4 (26H)

 Synthesis Example 25 (Synthesis of Compound (H-8))

 In a 50 Oml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 2.08 g (0.300 mol) of lithium metal and 100 mL of distilled THF were added. Was added, and a solution of 25.97 g (0.100 mol) of 2,2-bis (4-chlorophenyl) propane in 200 ml of distilled THF was added dropwise with vigorous stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation.

 In a 100-m 4-neck flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 137.42 g (0.600 mol) of para-naphthylphosphinyl dichloride was added. 300 ml of distilled THF was added thereto, and the mixture was stirred while gently flowing nitrogen, and the whole amount of the organic lithium compound solution was added at 0 to 5 over 3 hours from a dropping funnel. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess sodium naphthylphosphinyl dichloride were distilled off under reduced pressure. Add 300 ml of dry ethyl acetate to the residue and stir to remove residual salts by filtration. Evaporate the solution under reduced pressure to prepare 2,2-bis [4- (chloro-naphthylphosphiel) phenyl] propane. did.

'' A 3.000-m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 3.5.75 g (0.300 mol) of aminostyrene and 30. 36 g (0.300 mol) and 200 ml of THF were added, and at 0 to 5 ° C., the total amount of 2,2-bis [4- (chloro-naphthylphosphinyl) phenyl] propane described above was reduced. A 300 ml THF solution was added dropwise. After reacting at the temperature for 3 hours and at room temperature for 10 hours, about half of the solvent was distilled off under reduced pressure and poured into 1500 ml of water, and extracted with 150 ml of ethyl acetate five times.The ethyl acetate phase was sulfuric anhydride. Drying over sodium, filtration and evaporation under reduced pressure gave 69.46 g (yield 93%) of the desired compound. The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-8) described above.

Infrared absorption spectrum (cm— ¹ ): Le NH 3240, δ NH 1640, v ring 1605, 1495, v C = C 1630

 TOF-Mass spectrum (M / Z): 748, 749 (Calculated molecular weight = 746.8702)

R spectrum (δ, ppm): CH ₂ = 4.5 to 4.7 (4H), = CH-6.0 to 6.2 (2H),> NH 3.2 (2H), -CH ₃ 1.4 (6H), aromatic C- H 6.8-7.6 (30H)

 Synthesis Example 26 (Synthesis of Compound (Π-9))

 13.5.05 g (0.6000 mol) of biphenylphosphinyl dichloride in place of α-naphthylphosphinyl dichloride and N-aryl-jo-aminostyrene in place of aminostyrene (0.3 mol) Except that 47.77 g was used, 80.0 g (yield: 91%) of a target compound was obtained in the same manner as in Synthesis Example 25.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-9) described above.

 Infrared absorption spectrum (cm-R: V ring 1605, 1495, v C = C 1630

 TOF-Mass spectrum (M / Z): 881, 882 (Calculated molecular weight = 879.075)

NMR spectrum _{(, ppm): CH 2 =} 4.4~4.5 and 4 · 7~4.8 (8H), = CH - 5.4~5.5 and _{5.8~6.0 (4H), -CH 2 -} 2.8 (4H), -CH 3 1.4 (6H), Aromatic C-H 6.7-7.6 (34H) Synthesis Example 2 7 (Synthesis of Compound (Π-10))

 Phenylphosphinyl dichloride 71.39 g (0.600 mol) was used instead of phosphorus trichloride, and ^ chloromethylstyrene 45.79 g (0.3000) was used instead of aryl bromide. Mol) was used in the same manner as in Synthesis Example 18 to obtain 5.545 g (92% yield) of the target compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (Π-10) described above.

Infrared absorption spectrum (cm— ¹ ): So ring 1605, 1495, v C = C 1635

 TOF-Mass spectrum (M / Z): 604, 605 (Calculated molecular weight = 602.6940)

NMR spectrum (<5, ppm): CH 2 = 4 · 5~4 · 6 (4H), = CH- 5.5~5.6 (2Η), -CH 2 - 2.6 (4Η), aromatic CH 6.8~7.4 (26Η )

Synthesis Example 2 8 (Synthesis of Compound (Π—11)) 2.08 g (0.300 mol) of lithium metal pieces and 100 ml of distilled THF were placed in a 1000 m four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirring device, a nitrogen inlet tube, and a dropping funnel. Under vigorous stirring, a solution of 32.32 g (0.100 mol) of 4,4′-dichloro-1,1, -binaphthyl in 500 ml of distilled THF was added dropwise. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation, and the solvent was concentrated under reduced pressure to about twice the concentration.

 After this, 69.67 g (0.600 mol) of 2-hydroxyethyl acrylate and 60.71 g (0.600 mol) of triethylamine in THF 30 Om 70.50 g (yield: 91%) of the desired compound was obtained in the same manner as in Synthesis Example 18 except that one solution was used.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-11) described above.

Infrared absorption spectrum (cnf ¹ ): VC = 01720, v ring 1605, 1500, v C = C 1635, v COC 1060

 TOF-Mass spectrum (M / Z): 776,777 (Calculated molecular weight = 774.7036)

Image R spectrum (<5, ppm): CH 2 = 5.1~5.2 (8H), = CH- 6.0~6.2 (4H), -C00CH 2 CH 2 - 2.8~3.6 (16H), aromatic CH 6.8-7.7 ( 12H)

 Synthesis Example 29 (Synthesis of Compound (I [1-12]))

 4,4'-Bis (chlorophenyl phosphier) biphenyl was prepared in the same manner as in Synthesis Example 18 except that phenylphosphinyl dichloride was used in place of phosphorus trichloride, and the same procedure was repeated, except that phenylphosphinyl dichloride was used. did.

'' 38.45 g (0.300 mol) of N- (2-aminoethyl) methacrylamide and 30 ml of triethylamine in a 1 000m four-necked flask equipped with a reflux tube equipped with a drying tube, mechanical stirrer, nitrogen inlet tube, and dropping funnel 36 g (0.300 mol) of 400 ml of THF solution was added, and 0 to 5: 400 ml of THF solution containing 4,4′-bis (chlorophenylphosphier) biphenyl was added. It was dropped over time. The reaction was carried out at the same temperature for 4 hours and at room temperature for 12 hours. About half of the solvent was distilled off under reduced pressure, poured into 2000 ml of water, and extracted five times with 150 ml of ethyl acetate. The ethyl acetate phase was dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to give the desired compound (57.91, yield 93%). The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-12) described above.

 Infrared absorption spectrum (cm-RI: Li NH3240,3080, Amido-H 1645, Li ring 1605, 1495, vC = C 1630

 . TOF-Mass spectrum (M / Z): 624, 625 (Calculated molecular weight = 622.6876)

Negation R spectrum _{(δ, ppm): CH 2} = 4.6~5.0 (4H), -CH 2 - 2.6~3.4 (8H),> NH 3, 1,3.5 (4H), - CH 3 1.5 (6H ), Aromatic C-H 6.7 ~ 7.6 (18Η)

 Synthesis Example 30 (Synthesis of compound (H-13))

 In a 1000 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 4.16 g (0.600 mol) of lithium metal pieces and 200 ml of distilled THF were placed. Then, a solution of 44.62 g (0.200 mol) of 4,4'-dichlorobiphenyl in 400 ml of distilled THF was added dropwise with vigorous stirring. At this time, the dropping rate was adjusted so that a gentle boiling point reflux was maintained by the heat generated at the start of the reaction. The dropwise addition was completed in about 3 hours, and the mixture was refluxed at the boiling point for 1 hour. After cooling, excess metal lithium was removed by decantation. To this solution, a solution of 1.90 g (0.100 mol) of phenylphosphinyl dichloride in distilled THF 30 Om1 at 0 to 5 ° C. was added from a dropping funnel over 3 hours with vigorous stirring. . The mixture was reacted at the same temperature for 6 hours and at room temperature for 12 hours, and concentrated under reduced pressure to about 500 ml.

 A 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping port was charged with 200.13 ml of 82.39 g (0.600 mol) of phosphorus trichloride. The HF solution was added, and the above-mentioned concentrated solution was added at 0 to 5 ° C from a dropping funnel over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the solvent and excess phosphorus trichloride were distilled off under reduced pressure. 300 ml of dry ethyl acetate was added to the residue and stirred, the remaining salt was removed by filtration, and the solution was distilled off under reduced pressure. The residue was converted to a 50 Om 1 THF solution, reacted with an aryl magnesium bromide solution in the same manner as in Synthesis Example 18 and treated in the same manner to obtain 5.57 g of the desired compound (yield 87). Was.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (III-13) described above.

Infrared absorption spectrum (cur ¹ ): V ring 1605, 1495, Li OC 1635

TOF-Mass spectrum (M / Z): 640,641 (Calculated molecular weight = 638.7073) NMR scan Bae spectrum _{(δ, ppm): CH 2} = 4.6~4.7 (8Η), = CH- 5.3~5.6 (4Η), -CH 2 - 3.0 (8Η), aromatic CH 6.6~7.8 (21H)

 Synthesis Example 3 1 (Synthesis of Compound (H-20))

 Distillation of 1.90 g (0.100 mol) of phenylphosphinyl dichloride into a 100-m 4-neck flask equipped with a reflux tube equipped with a drying tube, a mechanical stirring device, a nitrogen inlet tube, and a dropping funnel Add 300 ml of THF, stir, cool to 0-5 ° C, and cool 5-5-neck 1-naphthol 35.72 g (0.200 mol) and triethylamine 25.30 g (0. A solution of 250 mol) in 300 ml of distilled THF was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the triethylamine hydrochloride was filtered off and evaporated to dryness under reduced pressure to quantitatively obtain bis (5-chloro-1-naphthoxide) phenylphosphinate. The whole amount was placed in a 100 ml four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping port, and stirred with a 400 ml solution of distilled THF. 5.0 g of lithium metal flakes were added over 3 hours while cooling. The reaction was carried out at the same temperature for 6 hours and at room temperature for 6 hours to obtain quantitatively bis (5-litho_1_naphthoxide) phenylphosphinate. Excess metal lithium was removed by decantation, and a solution of phosphorous trichloride (82.39 g, 0.600 mol) in 200 ml THF was added dropwise over 3 hours while cooling to 0 to 5 ° C. . After reacting at the same temperature for 3 hours and at room temperature for 3 hours, the solvent and excess phosphorus trichloride were distilled off under reduced pressure. The residue was converted to a 50 Oml THF solution, reacted with an allylmagnesium bromide solution in the same manner as in Synthesis Example 18, and treated in the same manner to give 58.779 g of the desired compound (yield 95%). Obtained.

 The measurements of the compound in the infrared absorption spectrum, T〇F_Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (Π-20) described above.

 Infrared absorption spectrum (cm-R: V ring 1606, 1500, v C = C 1640

 TOF_Mass spectrum (M / Z): 618, 619 (Calculated molecular weight = 616.6159)

NMR scan Bae spectrum (<5, ppm): CH 2 = 4.6~4.7 (8H), = CH - 5.3~5.6 (4H), _CH 2 - 3.0 (8H), aromatic CH 6.6~7.8 (17H)

 Synthesis Example 3 2 (Synthesis of Compound (Π—21))

In a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen introduction tube, and a dropping funnel, 47.68 g (0.3000 mol) of aryloxyphosphinyl dichloride was placed. Distillation THF 30 Om 1 is added and stirred, and cooled to 0 to 5 ° C while 1,5-naphthene is added. A solution of 16.02 g (0.100 mol) of evening diol and 25.30 g (0.250 mol) of triethylamine in 300 ml of distilled THF was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours. Triethylamine hydrochloride was removed by filtration and evaporated to dryness under reduced pressure to give quantitatively 1,5-bis (aryloxychlorophosphinoxy) naphthylene. . The whole amount was placed in a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, stirred as a distilled THF40 Om1 solution, and cooled to 0 to 5 ° C. Then, a solution of 35.72 g (0.200 mol) of 5_cloguchi-1-naphthol and 25.30 g (0.250 mol) of triethylamine in distilled THF 30 Om1 was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours. Triethylamine hydrochloride was removed by filtration, and dried under reduced pressure.

C 1 -Np-0-P (OCH ₂ CH = CH ₂ ) -Ο-Νρ-0-Ρ (OCH ₂ CH = CH ₂ ) -O-Np-C 1 (where Np is 1,5-naphthalene group ) Was obtained quantitatively.

 The whole amount was put in a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen introducing tube, and a dropping funnel as a solution of 40 Oml of distilled THF, and stirred at 0 to 5 ° C. With cooling, 5.0 g of lithium metal flakes were added over 3 hours. Reaction for 6 hours at the same temperature and 6 hours at room temperature

Li-Np-OP (OCH ₂ CH = CH ₂ ) -0-Np-0-P (OCH ₂ CH = CH ₂ ) -O-Np-Li (where Np is 1,5-naphthalene group) quantitative I got it. Excess metal lithium was removed by decantation, and a solution of 82.39 g (0.600 mol) of phosphorus trichloride in 20 Om 1 T HF was added dropwise over 3 hours while cooling to 0 to 5 ° C. After reacting at the same temperature for 3 hours and at room temperature for 3 hours, the solvent and excess phosphorus trichloride were distilled off under reduced pressure.

Cl ₂ P-Np-0-P (OCH ₂ CH = CH ₂ ) -0-Np-0-P (OCH ₂ CH = CH ₂ ) -0-Np-PCl ₂ (where Np is 1, 5_ Len group) was obtained quantitatively. The residue was stirred as a 50 Om 1 solution in THF and cooled to 0-5 ° C with 34.85 g (0.600 mol) of aryl alcohol and 60.72 g (0.600 mol) of triethylamine in 20 ml. The Om 1 THF solution was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and triethylamine hydrochloride was removed by filtration and dried under reduced pressure to obtain 85.24 g (yield 94%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (I [121]) described above.

Infrared absorption spectrum (cm— ¹ ): Le ring 1606, 1500, C = C 1640 TOF-Mass spectrum (M / Z): 910,911 (Calculated molecular weight = 908.8024)

Image R spectrum _{(δ, ppm): CH 2} = 4.6~4.7 (12H), = CH- 5.3~5 · 6 (6Η), - CH 2 - 3.0 (12H), aromatic CH 6 ·. 6 to 7.8 (18Η)

 Synthesis Example 3 3 (Synthesis of Compound (Π—22))

 In a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel, 42.88 g (0.300 mol) of diaryl phosphier dichloride was distilled THF. Add 300 ml, stir, and cool to 0-5 ° C while cooling p-hydroquinone 1 1.O lg (0.100 mol) and triethylamine 25.30 g (0.250 mol) A solution of distilled THF 30 Om1 was added dropwise over 3 hours. The reaction was allowed to proceed at the same temperature for 6 hours and at room temperature for 12 hours, and the toluenediamine hydrochloride was filtered off and dried under reduced pressure to give quantitatively 1,4-bis (arylchlorophosphinoxy) benzene. .

 The whole amount was placed in a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel as a solution of 40 Oml of distilled THF, and stirred at 0 to 5 ° C. A solution of 34.2 g (0.200 mol) of 4_bromophenol and 25.30 g (0.250 mol) of triethylamine in THF 30 Om1 was added dropwise over 3 hours while cooling the mixture. did. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and triethylamine hydrochloride was removed by filtration.

Br- φ -0-P (CH ₂ CH = CH ₂ ) -0- -0-P (CH ₂ CH = CH ₂ ) -0- -Br (φ is 1,4-phenylene group) Obtained quantitatively.

 The whole amount was put into a 100 Om four-necked flask equipped with a reflux tube equipped with a drying tube, a mechanical stirrer, a nitrogen inlet tube, and a dropping funnel as a solution of 40 Oml of distilled THF, and stirred at 0 to 5 ° C. 5.0 g of lithium metal flakes were added over 3 hours while cooling. Reaction at the same temperature for 6 hours and room temperature for 6 hours

L i--0-P (CH ₂ CH = CH ₂ ) -0- φ -0-P (CH ₂ CH = CH ₂ ) -0- -L i (where φ is 1,4-phenylene group) Was quantitatively obtained. Excess metal lithium is removed by decantation, and a solution of 82.39 g (0.600 mol) of phosphorus trichloride in 20 Om 1 T HF is added dropwise over 3 hours while cooling to 0 to 5 ° C. did. After reacting at the same temperature for 3 hours and at room temperature for 3 hours, the solvent and excess phosphorus trichloride were distilled off under reduced pressure.

C 1 ₂ Ρ- φ -0-P (CH ₂ CH = CH ₂ ) -0- φ -0-P (CH ₂ CH = CH ₂ ) -0- -PC 1 ₂ (However, φ is 1,4- Diene group) was obtained quantitatively. The residue is stirred as a 500 ml THF solution and cooled to 0-5 ° C while 34.26 g (0.6000 mol) of arylamine and 0.60.7 g (0.600 mol) of triethylamine are added. Was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the triethylamine hydrochloride was removed by filtration and dried under reduced pressure to obtain 62.29 g of the desired compound (yield: 93%).

 The measurements of the compound in the infrared absorption spectrum, TOF-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (II-22) described above.

Infrared absorption spectrum (cnf ¹ ): ring 1604, 1496, v C = C 1635

 TOF-Mass spectrum (M / Z): 668, 669 (Calculated molecular weight = 666.6546)

NMR spectrum _{(δ, ppm): CH 2} = 4.4~4.7 (12H), = CH- 5.2~5 · 6 (6Η), -CH 2 - 3.0 ~3.7 (12H), aromatic CH 6.6~7.8 (12H)

 Synthesis Example 34 (Synthesis of compound (Π—23))

 Similarly to Synthesis Example 33,

C 1 ₂ Ρ- φ -0-Ρ (CH ₂ CH = CH ₂ ) -0- φ -0-P (CH ₂ CH = CH ₂ ) -0- -PC 1 ₂ (However, φ is 1,4- Diene group) was obtained quantitatively. Thereafter, instead of 7-lylamine, a solution of 58.30 g (0.600 mol) of diarylamine and 60.72 g (0.600 mol) of triethylamine in 20 Om 1 THF was added dropwise over 3 hours. The reaction was carried out at the same temperature for 6 hours and at room temperature for 12 hours, and the triethylamine hydrochloride was filtered off and dried under reduced pressure to obtain 79.54 g (yield 96%) of the desired compound.

 The measurements of the compound in the infrared absorption spectrum, T-F-Mass spectrum, and NMR resulted in the followings. Thus, the measurements identified the structure of Compound (III-23) described above.

Infrared absorption spectrum (cm- ¹ ): V ring 1605, 1495, Li OC 1635

'' TOF-Mass spectrum (M / Z): 828, 829 (Calculated molecular weight = 826.9130)

Anonymous R spectrum _{(δ, ppm): CH 2} = 4.4~4.7 (20 ©, = CH- 5.2~5.6 (10H), -CH 2 - 3.0 ~3.8 (20H), aromatic CH 6.6-7.8 (12H )

 [Production of flame-retardant resin products using reactive flame retardants of general formula (I)]

 Example 1

66.3 Nylon as a thermoplastic resin (Ube Industries, Ltd .: 2123B) 56.3 parts by mass, glass fiber with a fiber length of about 3 mm surface-treated with a silane coupling agent as a reinforcing fiber (Asahi Fiberglass Co., Ltd.) : 03. JAFT2Ak25) 25 parts by mass, car pump as colorant 0.5 parts by weight of a rack, 0.2 parts by weight of an antioxidant (manufactured by Ciba Geigy Co., Ltd .: Irganoylurganox 10 10), 5 parts by weight of talc having a particle size of 2 as an inorganic filler and a crane having a nano particle size (Nissho Iwai Bentonite Co., Ltd. Nanomat 1.30T) 3 parts by mass, and 10 parts by mass of the above compound (1-20) as a reactive flame retardant were blended into a side-flow twin-screw extruder (Nippon Steel Corporation) Resin pellets obtained by kneading at 28 ° C and drying at 105 ° C for 4 hours. The above pellets were resin-sealed at 280 ° C using an injection molding machine (FUNUC: a50C). C, Molded at a mold temperature of 80 ° C.

 Thereafter, the molded product was irradiated with 25 kGy of α-ray using cobalt 60 as a radiation source to obtain a resin processed product of Example 1.

 Example 2

 As a thermoplastic resin, 66 nylon (Ube Industries, Ltd .: 2020 B) 55.3 parts by mass, glass fiber with a fiber length of about 3 mm surface-treated with a silane coupling agent as a reinforcing fiber (Asahi Fiberglass Corporation: 03 JAFT2Ak 25) 25 parts by mass, 0.5 parts by mass of a car pump rack as a colorant, 0.2 parts by mass of an antioxidant (manufactured by Ciba-Geigy Co., Ltd .: Irganoylurganox 10 10), 2 parts by mass of an inorganic filler having a particle size of 2 5 parts by weight of talc and a nano-sized clay (Nanosho 1.30T manufactured by Nissho Iwai Bentonite Co., Ltd.). 3 parts by weight, and 12 parts by weight of the above compound (1-14) as a reactive flame retardant were blended. After kneading at 280 ° C with a side-flow type twin screw extruder (manufactured by Nippon Steel Corporation) to obtain resin pellets and drying at 105 ° C for 4 hours, the above pellets are injected into an injection molding machine (FUNUC: Q ( Molding was performed using 50 C) at a resin temperature of 280 and a mold temperature of 80 ° C.

 Thereafter, the molded article was irradiated with 25 kGy of γ-rays using cobalt 60 as a radiation source to obtain a resin processed article of Example 2.

-Example 3

 Nylon 66 as thermoplastic resin (57.2 parts by mass of Ube Industries, Ltd .: 2020 B), 4 parts by mass of the above talc as an inorganic filler, and clay of nano-particle size (Nissho Iwai Bentonite Co., Ltd. 1.30T) 3 parts by weight, 0.5 parts by weight of a pump rack as a colorant, 8 parts by weight of the above compound (I-13) and 6 parts by weight of a compound (I-1) as a reactive flame retardant, antioxidant 0.3 parts by mass of an agent (manufactured by Ciba-Geigy Co., Ltd .: Irganox 101) was added and mixed.

Melt the above mixture using a side flow type twin screw extruder set at 280 ° C, Furthermore, 20 parts by mass of glass fiber (Asahi Fiber One Glass Co., Ltd .: 03.JAFT2Ak25) with a fiber length of about 3 mm and surface-treated with a silane coupling agent as a reinforcing fiber was melted from the side by extrusion kneading. After mixing with the mixture to obtain a compound pellet, the pellet was dried at 105 ° C for 4 hours.

 Using an injection molding machine (FUNUC: α 50C), a general cylinder temperature of 280 ° C, mold temperature of 80 ° C, injection pressure of 78.4 MPa, injection speed of 120 mmZ s, and cooling time of 15 seconds Under the conditions, electric and electronic parts and molded products for automobiles were molded.

 Thereafter, the molded product was irradiated with 25 kGy of α-ray using cobalt 60 as a radiation source to obtain a resin processed product of Example 3.

 Example 4

 Nylon 66 as thermoplastic resin (56.2 parts by mass; Ube Industries, Ltd .: 2020 B) 56.2 parts by mass, 11 parts by mass of the above compound (I_22) as reactive flame retardant and non-reactive organophosphorus flame retardant (Sanko Chemical (BCA) The resin processed product of Example 4 was obtained under the same conditions as in Example 3 except that 5 parts by mass was used.

 Example 5

 55.2 parts by mass of 66 nylon as thermoplastic resin (manufactured by Ube Industries, Ltd .: 2020 B), 4 parts by mass of nano-sized clay used in Example 2 as an inorganic filler, 0.5 parts by mass of car pump rack as a coloring agent Parts, 10 parts by weight of the above compound (I-18) as a reactive flame retardant, 2 parts by weight of a polyfunctional cyclic compound (TAIC, manufactured by Nippon Kasei Co., Ltd.), and organic phosphorus-based flame retardant (BCA, manufactured by Sanko Chemical Co., Ltd.) 7 Parts by mass, 0.3 parts by mass of an antioxidant (manufactured by Ciba-Geigy Corporation: Irganox 1010) were added and mixed.

 The above mixture was melted using a side-flow type twin-screw extruder set at 280 ° C, and a glass fiber with a fiber length of about 3 mm (Asahi Fiberglass) treated with a silane coupling agent as a reinforcing fiber 20 parts by mass of the compound: 03.JAFT2Ak25) were mixed with the above mixture melted from the side by extrusion kneading to obtain a compound pellet, and the pellet was dried at 105 ° C for 4 hours.

 Using an injection molding machine (manufactured by FUNUC: 50C), the general conditions of cylinder temperature 280 ° (, mold temperature 80 ° C, injection pressure 78.4MPa, injection speed 120mmZs, cooling time 15 seconds) The company formed electrical and electronic parts and molded products for automobiles.

After that, the above molded product was irradiated with 25 kGy of α-ray with cobalt 60 A resin processed product of Example 5 was obtained.

 Example 6

55.3 parts by mass of polybutylene terephthalate resin (Toray Industries, Ltd .: Trecon 1401 X06) as a thermoplastic resin, 10 parts by mass of the above compound (I_23) as a reactive flame retardant, non-reactive organophosphorus 5 parts by mass of flame retardant (manufactured by Sanko Chemical Co., Ltd .: BCA), 2 parts by mass of polyfunctional cyclic compound (manufactured by Toagosei Co., Ltd .: M-315), 4 parts by mass of the nano-sized particle clay of Example 2 as an inorganic additive 20 parts by weight of the glass fiber of Example 1 as a reinforcing agent, 0.5 parts by weight of a power pump rack as a coloring agent, an antioxidant (manufactured by Ciba-Geigy Co., Ltd .: Irganoilganox 10 10) 0.2 using mass parts, after obtaining the resin compound pellet kneaded kneading temperature at 245 ° C, dried for 3 hours at 130 ° C, the cylinder at the time of molding - except for changing the temperature condition of ₂ 50 ° C A molded article was molded under the same conditions as in Example 3.

 Thereafter, the molded product was irradiated with an electron beam having an irradiation voltage of 40 kGy at an acceleration voltage of 4.8 MeV using an accelerator manufactured by Sumitomo Heavy Industries, Ltd. to obtain a resin processed product of Example 6.

 Example 7

 A molded article was molded under the same conditions as in Example 3 except that 3 parts by mass of a thermal catalyst (NOFMER BC, manufactured by NOF CORPORATION) was further added to the system of Example 3.

 Thereafter, the molded product was reacted by heating at 245 for 8 hours to obtain a processed resin product of Example 7.

 Example 8

 The same procedure as in Example 5 except that 7 parts by mass of an ultraviolet initiator (2: 1 mixture of Irganox 651 and Irganox 369 manufactured by Ciba Geigy) was added to the system of Example 5, t: 0.6 mm thickness) A molded article was molded.

Thereafter, the molded article was irradiated with an ultra-high pressure mercury lamp at a wavelength of 365 nm at an illuminance of 15 OmWZcm ² for 2 minutes to obtain a resin processed article of Example 8.

 Example 9

Thermosetting epoxy-based mold resin (manufactured by Nagase Chemical Co., Ltd., main agent XNR4012: 100, curing agent XNH4012: 50, curing accelerator FD400: 1) 45 parts by mass of silica dispersed in 45 parts by mass After adding 10 parts by mass of the above compound (I-117) as a flame retardant, a molded article was obtained, and then reacted at 100 ° (for 1 hour) to process the resin processed product of Example 9 (sealing agent). Got.

 Example 1 0

 Epoxy resin for semiconductor encapsulation (Shin-Etsu Chemical Co., Ltd .: Semicoat 1 15) After adding 92 parts by mass of the above compound (1-1-5) as a reactive flame retardant, 8 parts by mass to obtain a molded product , 150: The reaction was carried out for 4 hours to obtain a resin processed product of Example 10 (sealing agent). Comparative Example 1-: 0

 In Examples 1 to 10, resin-processed products of Comparative Examples 1 to 10 were obtained in the same manner as in Examples 1 to 10, except that the reactive flame retardant of the present invention was not blended.

 Comparative Example 1 1

 Comparative Example 11 was prepared in the same manner as in Example 5 except that only 20 parts by mass of a non-reactive organophosphorus flame retardant (manufactured by Sanko Chemical Co., Ltd .: BCA) was added as the flame retardant. A fat additive was obtained.

 [Manufacture of flame-retardant resin products using reactive flame retardants of general formula (Π)]

 Example 11

 As a thermoplastic resin, 66 nylon (Ube Industries, Ltd .: 2 123 Β) 59.3 parts by mass, glass fiber with a fiber length of about 3 mm surface-treated with a silane coupling agent as a reinforcing fiber (Asahi Fiberglass Corporation: 03 JAFT2Ak25) 25 parts by mass, 0.5 parts by mass of a power pump rack as a colorant, 0.2 parts by mass of an antioxidant (manufactured by Ciba Geigy Corporation: 0.2 g) 5 parts by mass of talc with a diameter of 2 m and 10 parts by mass of the above compound (Π-23) as a reactive flame retardant are mixed and kneaded at 280 ° C with a side-flow twin-screw extruder (manufactured by Nippon Steel Corporation). After drying the resin pellets at 105 ° C for 4 hours, the above pellets were injected into an injection molding machine (FUNUC Co., Ltd., using resin 500 at a resin temperature of 280 ° C and a mold temperature of 80 ° C). Molded.

 Thereafter, the molded product was irradiated with 25 kGy of α-ray using cobalt 60 as a radiation source to obtain a resin-processed product of Example 11.

 Example 12.

As a thermoplastic resin, 66 nylon (Ube Industries, Ltd .: 2020 B) 56. 3 parts by mass, glass fiber with a fiber length of approximately 3 mm surface-treated with a silane coupling agent as a reinforcing fiber. (Asahi Fiber One Glass: 03 JAFT2Ak25) 25 parts by mass, 0.5 parts by mass of a car pump rack as a colorant, an antioxidant (manufactured by Ciba-Geigy Co., Ltd .: ilganoilganox 10) 1 0) 0.2 parts by mass, 5 parts by mass of talc having a particle size of 2 m as an inorganic filler, and 2 parts by mass of clay having a nano particle size (Nitamer 1.30T manufactured by Nissho Iwai Bentonite Co., Ltd.), reactivity 11 parts by mass of the above compound (H-3) was blended as a flame retardant, and kneaded at 280 ° C with a side-flow type twin screw extruder (manufactured by Nippon Steel Corporation) to obtain resin pellets, and 105 ° (:, After drying for 4 hours, the pellets were molded using an injection molding machine (manufactured by FUNUC: CK50C) under the conditions of a resin temperature of 280 and a mold temperature of 80 ° C.

 Thereafter, the molded article was irradiated with γ-rays of 25 kGy using cobalt 60 as a radiation source to obtain a resin processed article of Example 12.

 Example 13

 Nylon 66 as thermoplastic resin (57.2 parts by mass of Ube Industries, Ltd .: 2020 B), 4 parts by mass of the above talc as an inorganic filler, and clay of nano-particle size (Nissho Iwai Bentonite Co., Ltd. 1.30T) 3 parts by mass, 0.5 parts by mass of Ripbon Black as a colorant, 9 parts by mass of the above compound (Π-20) and 5 parts by mass of compound (Π-8) as a reactive flame retardant, antioxidant 0.3 parts by mass of an agent (manufactured by Ciba-Geigy Corporation: Irganox 1010) was added and mixed.

 The above mixture was melted using a side-edge type twin-screw extruder set at 280, and a glass fiber with a fiber length of about 3 mm (surface of Asahi Fiber Glass Co., Ltd.) was treated with a silane coupling agent as a reinforcing fiber. Manufacture: 03. JAFT2Ak25) 20 parts by mass were mixed with the above mixture melted from the side using extrusion kneading to obtain a compound pellet, and the pellet was dried at 105 ° C for 4 hours.

 General conditions of cylinder temperature 280 ° C, mold temperature 80 ° C, injection pressure 78.4MPa, injection speed 120mm / s, cooling time 15 seconds using an injection molding machine (FUNUC: 50C) The company formed molded products for electric and electronic parts and automobiles.

 Thereafter, the above molded product was irradiated with τ-rays of 25 kGy using cobalt 60 as a radiation source to obtain a resin processed product of Example 13.

 Example 14

56.2 parts by mass of 66 nylon as thermoplastic resin (manufactured by Ube Industries, Ltd .: 2020 B), 11 parts by mass of the above compound (Π-14) as reactive flame retardant, and non-reactive organophosphorus flame retardant (III A resin processed product of Example 14 was obtained under the same conditions as in Example 13 except that 5 parts by mass of photochemical company: BCA) was used. Example 15

 55.2 parts by mass of 66 nylon as thermoplastic resin (manufactured by Ube Industries, Ltd .: 2020 B), 4 parts by mass of nano-sized clay used in Example 2 as an inorganic filler, 0.5 parts by mass of car pump rack as a coloring agent Part, 10 parts by weight of the above compound (反 応 -8) as a reactive flame retardant, 2 parts by weight of a polyfunctional cyclic compound (manufactured by Nippon Kasei Co., Ltd .: TAIC), organophosphorus flame retardant (HCA-HQ, manufactured by Sanko Chemical Co., Ltd.) 8 parts by mass and 0.3 parts by mass of an antioxidant (manufactured by Ciba-Geigy Corporation: Irganox 1010) were added and mixed.

 The above mixture was melted using a side-flow type twin-screw extruder set at 280 ° C, and glass fibers with a fiber length of about 3 mm (Asahi Fiber Glass Co., Ltd.) were surface-treated with silane coupling agents as reinforcing fibers. After mixing 20 parts by mass of the above mixture melted from the side using extrusion kneading to obtain a compound pellet, the pellets were dried at 105 ° C for 4 hours.

 Using an injection molding machine (FUNUC: 50 C), general conditions of cylinder temperature 280 ° C, mold temperature 80 ° C, injection pressure 78.4MPa, injection speed 120mm / s, cooling time 15 seconds The company formed molded products for electric and electronic parts and automobiles.

 Thereafter, the molded product was irradiated with a k-ray of 25 kGy using cobalt 60 as a radiation source to obtain a resin processed product of Example 15.

 Example 16

 Polybutylene terephthalate resin as thermoplastic resin (Toray Co., Ltd .: Trecon 1401 X06) 53.3 parts by mass, the above compound (Π-21) as reactive flame retardant 10 parts by mass, non-reactive organophosphorus 7 parts by mass of flame retardant (manufactured by Sanko Chemical Co., Ltd .: BCA), 2 parts by mass of polyfunctional cyclic compound (manufactured by Toagosei Co., Ltd .: M-315), 4 parts by mass of nano-sized particles of Example 12 as an inorganic additive 20 parts by weight of the glass fiber of Example 11 as a reinforcing agent, 0.5 parts by weight of a power pump rack as a coloring agent, and an antioxidant (manufactured by Ciba-Geigy Corporation; Using 2 parts by mass, kneading at 245 ° C kneading temperature to obtain resin compound pellets, drying at 130 ° C for 3 hours, and changing the cylinder temperature during molding to 250 ° C A molded article was molded under the same conditions as in Example 13 except that the above procedure was performed.

Thereafter, the molded article was irradiated with an electron beam having an irradiation voltage of 40 kGy at an acceleration voltage of 4.8 MeV using an accelerator manufactured by Sumitomo Heavy Industries, Ltd. to obtain a resin processed article of Example 16. Example 17

 A molded article was molded under the same conditions as in Example 13 except that 3 parts by mass of a thermal catalyst (NOFMER BC, manufactured by NOF CORPORATION) was further added to the system of Example 13.

 Thereafter, the molded product was reacted by heating at 245 ° C. for 8 hours to obtain a resin processed product of Example 17.

 Example 18

 A thin wall (t: 0.6) was obtained in the same manner as in Example 15 except that 7 parts by mass of an ultraviolet initiator (2: 1 mixture of Irganox 651 and Irganox 369 manufactured by Ciba Geigy) was added to the system of Example 15. mm thickness) A molded product was molded.

Thereafter, the molded article was irradiated with an ultra-high pressure mercury lamp at a wavelength of 365 nm at an illuminance of 15 OmWXcm ² for 2 minutes to obtain a resin processed article of Example 18.

 Example 19

 Thermosetting epoxy mold resin (Nagase Chemical Co., Ltd., main agent XNR4012: 100, curing agent XNH4012: 50, curing accelerator FD400: 1) 45 parts by mass of silica dispersed in 45 parts by mass as a reactive flame retardant After adding 10 parts by mass of the above compound (II-11) to obtain a molded molded product, the molded product was reacted at 100 ° C. for 1 hour to obtain a processed resin product of Example 19 (sealing agent).

 Example 20

 Epoxy resin for semiconductor encapsulation (Shin-Etsu Chemical Co., Ltd .: Semicoat 1 15) 92 parts by mass of the above compound (Π-15) as a reactive flame retardant was added 8 parts by mass to obtain a molded product The mixture was reacted at 150 ° C. for 4 hours to obtain a resin processed product (sealing agent) of Example 20. Comparative Examples 12 to 21

 In Examples 11 to 20, resin-processed products of Comparative Examples 12 to 21 were obtained in the same manner as in Examples 11 to 20, except that the reactive flame retardant of the present invention was not blended. Comparative Example 22

 Comparative Example 22 was prepared in the same manner as in Example 15 except that only 20 parts by mass of a non-reactive ft organophosphorus flame retardant (manufactured by Sanko Chemical Co., Ltd .: HCA-HQ) was added as the flame retardant. A resin processed product was obtained.

 Test example

For the resin processed products of Examples 1 to 20 and Comparative Examples 1 to 22, UL One 94-inch test piece (5 inches long, 1/2 inch wide, 3.2 mm thick) and a glow-wire test piece (60 mm square) according to the IEC 60695-2 method (GWF I) , Thickness 1.6 mm), and were subjected to UL 94 test, glow wire test (IEC compliance), and solder heat resistance test. In addition, a pre-out test at 300 ° C for 3 hours was performed for all resin processed products.

 In the UL 94 test, the test specimen was mounted vertically, and the burning time after flame contact for 10 seconds with a Bunsen burner was recorded. In addition, the second 10-second indirect flame after the fire extinguishing and the burning time after the flame contact is recorded again. It was determined by the presence or absence of an object.

 In the glow wire test, a 4mm diameter nichrome wire (component: nickel 80%, chromium 20%) bent as a glow wire so that the tip is not broken, and a 0.5mm diameter thermocouple for temperature measurement The test was performed using K (Chromel-Alumel) at a thermocouple crimping load of 1.0 ± 0.2 N and a temperature of 850 ° C. The criteria for flammability (GWF I) were based on the fact that the burning time after contact for 30 seconds was within 30 seconds and that the tissue paper under the sample did not ignite.

 The solder heat resistance test showed the dimensional deformation rate after immersion in a solder bath at 350 ° C for 10 seconds.

The results are summarized in Tables 1 and 2.

Table 2

From the results in Tables 1 and 2, the flame retardancy of the resin-processed products of the examples was as excellent as V-0, all passed the glow wire test, and the dimensional deformation after the solder heat test. It can be seen that the rate is less than 26%. Even after 3 hours at 300 ° C, no bleeding out of forsythia was observed.

On the other hand, Comparative Example 110 and Comparative Example 1221, which do not contain the reactive flame retardant of the present invention, It was found that the flame retardancy was insufficient with that of HB, and all were unacceptable in the glow-wire test, and the dimensional deformation rate after the soldering heat test was inferior to that of the examples. Further, in Comparative Examples 11 and 22 in which a non-reactive organophosphorus flame retardant was used as a flame retardant, the flame retardancy was insufficient at V-2, and after 3 hours at 300 ° C. Bleed-out of the flame retardant was observed. Industrial applicability

 INDUSTRIAL APPLICABILITY The present invention is suitable as a halogen-free non-octogen flame retardant and a flame-retardant resin processed product for resin molded products such as electric parts and electronic parts, sealing agents for semiconductors and the like, coating films and the like. Available to

Claims

Sought

1. A reactive flame retardant having reactivity with a resin and imparting flame retardancy by binding to the resin by the reaction, and represented by the following general formula (I) or (H): Reactive flame retardant characterized by containing an organic phosphorus compound having an unsaturated group at the terminal

R 'R ³ R ⁴

-ΑΓΪ ~~ t ^p一^Ar i ~ "P… (Π)

R ^z "R ⁵

(In the formula (I) or (Π), each molecule contains at least one P—C bond, and A and Ar ₂ are each a bifunctional aromatic containing 20 or less carbon atoms and free of mobile hydrogen.) Represents a hydrocarbon group, and n is an integer of 0 to 2. ¹ to! ^ ⁵ are one NHC H ₂ CH = CH ₂ , one N (CH ₂ CH = CH ₂ ) ₂ , CH ₂ CH 2 CH ₂ , CH ₂ CH = CH ₂ , CH ₂ CH ₂ OCH = CH ₂ , _ (C ₆ H ₄ ) — CH = CH ₂ , — 0 (C ₆ H ₄ ) — CH = CH ₂ , —CH ₂ (C ₆ H ₄ ) —CH = CH ₂ , —NH (C ₆ H ₄ ) —CH = CH ₂ , N (CH ₂ CH = CH ₂ ) — (C ₆ H ₄ ) CH = CH ₂ , — O— R-O〇 C— C (R,) = CH ₂ , -NH-R-NHCO-C (R ') = CH ₂ , or from an aryl group with 12 or less carbon atoms Here, R represents an alkylene group having 2 to 5 carbon atoms, R ′ represents hydrogen or a methyl group, and at least one of ¹ to! ^ ⁵ has one CH = CH ₂ group or one C (CH ₃ ) = Including CH ₂ group.)

 2. After the resin composition containing the reactive flame retardant according to claim 1 and a resin is solidified, the resin and the reactive flame retardant are reacted with each other by heating or irradiation with radiation, and the flame retardant is ferocious. A flame-retardant resin processed product, comprising the reactive flame retardant in an amount of 1 to 20% by mass based on the entire flame-retardant resin processed product.

3. The resin composition contains two or more reactive flame retardants, and at least one reactive flame retardant 3. The flame-retardant resin processed product according to claim 2, wherein the class is a polyfunctional reactive flame retardant.

4. The resin composition according to claim 2 or 3, wherein the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant is a cyclic nitrogen-containing compound having at least one unsaturated group at a terminal. A flame-retardant resin product as described.

 5. The resin composition according to any one of claims 2 to 4, wherein the resin composition further contains a flame retardant other than the reactive flame retardant, and the flame retardant is an addition-type flame retardant having no reactivity. A flame-retardant resin product as described.

 6. The resin composition further comprises a crosslinking agent having no flame retardancy but having reactivity with the resin, wherein the crosslinking agent has a polyfunctional monomer having an unsaturated group at a terminal of a main skeleton. The flame-retardant resin processed product according to any one of claims 2 to 5, which is an oligomer or an oligomer.

 7. The flame-retardant resin processed product according to any one of claims 2 to 6, comprising 1 to 35% by mass of an inorganic filler with respect to the entire flame-retardant resin processed product.

 8. The method according to claim 7, wherein the inorganic filler comprises a layered clay formed by laminating a silicide layer, and the layered clay is contained in an amount of 1 to 10% by mass based on the entire flame-retardant resin processed product. A flame-retardant resin product as described.

 9. The flame-retardant resin processed product according to any one of claims 2 to 8, comprising 5 to 40% by mass of a reinforcing fiber with respect to the whole of the flame-retardant resin processed product.

 10. The flame retardant according to any one of claims 2 to 9, wherein the resin and the reactive flame retardant are obtained by reacting by irradiation with an electron beam or an α-ray at a dose of 10 kGy or more. Processed resin.

 11.The flame retardant according to any one of claims 2 to 9, wherein the resin and the reactive flame retardant are obtained by reacting at a temperature 5 ° C or more higher than a temperature at which the resin composition is molded. Processed resin.

 12. The flame-retardant resin processed product according to any one of claims 2 to 11, wherein the processed flame-retardant resin product is one selected from a molded product, a coating film, and a sealant. .

 13. The flame-retardant resin processed product according to any one of claims 2 to 12, wherein the processed flame-retardant resin product is used as an electric component or an electronic component.