JP2013249374A - Phosphoric ester compound and flame retardant including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound capable of developing excellent flame retardancy and suppressing reduction in mechanical strength even when blended in a resin.SOLUTION: A phosphoric ester compound is represented by chemical formula (1) (In the formula: R, R, R, and Rare each a 1-20C alkyl group, a 6-20C aryl group, or an organic group having a reactive double bond, and at least one of R, R, R, and Ris the organic group having a reactive double bond; Rand Rare each independently a hydrogen atom or a methyl group; A is a 2-4C alkylene group; m and n are each independently an integer of 1-15; a, b, c, and d are each independently 0 or 1; X is a halogen atom; e and f are each independently an integer of 0-4; and p is an integer of 1-5).

Description

  The present invention relates to a phosphate ester compound and a flame retardant containing the same.

  Thermoplastic resins such as polyolefin resins and polyester resins, and thermosetting resins such as epoxy resins have excellent moldability, mechanical strength, and electrical properties as general-purpose resins and engineering plastics. Widely used in various fields including the electronic field. And the resin processed product etc. which processed and shape | molded these are requested | required of a flame retardance from the viewpoint of safety aiming at the fire prevention by high temperature.

  In general, it is known that phosphorus and halogen-containing substances are effective for making such processed resin products flame-retardant. Phosphorus-based flame retardants and halogen-based flame retardants are added to the resin. It gives flame resistance to processed products. It is also known that when using phosphorus and a halogen-based flame retardant, flame retardancy is improved by a synergistic effect with phosphorus atoms.

  For example, Patent Document 1 discloses that a piperazine salt of an acidic phosphate ester having a phosphorinane structure or an alkylenediamine salt having 1 to 6 carbon atoms is used as a flame retardant. Further, Patent Document 2 discloses a flame retardant for a resin mainly composed of a salt composed of an aromatic phosphate such as monophenyl phosphate and monotolyl phosphate and an aliphatic amine such as piperazine.

  Furthermore, Patent Document 3 discloses a flame retardant effect that exhibits excellent flame retardant effects as a halogen-free flame retardant formulation, and is excellent in heat resistance and water resistance of molded articles, and also has excellent adhesion in electrical laminate applications. It is disclosed that a phosphorus-containing phenol compound is used as a flame retardant for obtaining an epoxy resin.

JP 2002-20394 A JP 2002-80633 A JP 2002-138096 A

  However, the flame retardants described in Patent Documents 1 to 3 are insufficient in flame retardancy, and it is necessary to increase the blending amount in the resin. Moreover, the film obtained after mix | blending the said flame retardant with resin from the rigidity of the flame retardant molecule | numerator and the low compatibility with resin had the problem that it became brittle.

  Then, this invention aims at providing the novel compound which expresses the outstanding flame retardance and can suppress the fall of mechanical strength, even if it mix | blends with resin.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, the present inventors have found that the above problems can be solved by a phosphate ester compound having a reactive double bond and having an alkylene oxide chain at a specific site, and has completed the present invention.

  That is, the present invention is a phosphate ester compound represented by the following chemical formula (1).

In the chemical formula (1),
R ¹ , R ² , R ³ , and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or non-substituted group. A substituted aryl group having 6 to 20 carbon atoms or an organic group having a reactive double bond, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ has a reactive double bond An organic group,
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group,
A is an alkylene group having 2 to 4 carbon atoms,
m and n are each independently an integer of 1 to 15,
a, b, c, and d are each independently 0 or 1,
X is a halogen atom,
e and f are each independently an integer of 0 to 4,
p is an integer of 1-5.

  ADVANTAGE OF THE INVENTION According to this invention, the phosphate compound which expresses the outstanding flame retardance and can suppress the fall of mechanical strength even if it mix | blends with resin can be provided. Moreover, a flame retardance can also be provided to a base material by apply | coating the monomer mixture containing the phosphate ester compound of this invention to the surface of a base material, and making it harden | cure with an ultraviolet-ray etc.

  Hereinafter, the phosphate compound of the present invention will be described in detail.

  The present invention is a phosphate compound represented by the following chemical formula (1).

In the chemical formula (1),
R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C 1-20 linear or branched alkyl group, substituted or unsubstituted. An aryl group having 6 to 20 carbon atoms, or an organic group having a reactive double bond, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is an organic group having a reactive double bond Group,
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group,
A is an alkylene group having 2 to 4 carbon atoms,
m and n are each independently an integer of 1 to 15,
a, b, c, and d are each independently 0 or 1,
X is a halogen atom,
e and f are each independently an integer of 0 to 4,
p is an integer of 1-5.

  The phosphate ester compound of the present invention has a bisphenol structure, and by having a polyalkylene oxide structure, the viscosity of the phosphate ester compound of the present invention is reduced, compatibility with the resin, workability, And the flexibility of the membrane is further improved. In particular, in the case of a compound having a bromine atom in the bisphenol skeleton, flame retardancy is greatly improved due to a synergistic effect with a phosphorus atom.

  In addition, the phosphate ester compound of the present invention has a reactive double bond, but at the same time has a polyalkylene oxide structure, so the molecular flexibility is improved. The reaction rate of the resin having the phosphoric acid ester compound having the reactive double bond of the present invention is improved. Therefore, the mechanical properties of the resin can be improved by crosslinking the resin and the phosphate ester compound. In addition, it is possible to prevent bleed-out of the flame retardant present in an uncrosslinked state.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms used for R ¹ , R ² , R ³ , and R ⁴ in the chemical formula (1) include, for example, a methyl group and an ethyl group N-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-amyl group, t-pentyl group, neopentyl group, n-hexyl group 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethyl Butyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1- (n -Propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl Group, n-octyl group, 2-ethylhexyl group, 2-methylhexan-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2,2- Dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane -3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3-methylhepta -3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1, 1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl Group, 2,4,4-trimethylpentyl group, 2,3,4-trimethylpentan-3-yl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group N-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pen Group, 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 3,5,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, isodecyl group 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, 3,7-dimethyloctane-3-yl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, isododecyl group, 2- (n-butyl) octyl group, 2,3,4,6,6-pentamethylheptan-3-yl Group, n-tridecyl group, isotridecyl group, n-tetradecyl group, isotetradecyl group, 2- (n-hexyl) octyl group, 1-methyltridecyl group, n-pentadecyl group, isope Ntadecyl group, 3,7,11-trimethyldodecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, isostearyl group, n-nonadecyl group, n-eicosadecyl group, 3,7,11,15- A tetramethylhexadecyl group etc. are mentioned. Preferably, they are an ethyl group, n-propyl group, and 2-ethylhexyl group.

Examples of the aryl group having 6 to 20 carbon atoms used for R ¹ , R ² , R ³ , and R ⁴ in the chemical formula (1) include, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, 2- Naphtyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, mesityl group, pentarenyl Group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group Senyl group, Quarter anthracenyl group, Ant Examples include a laquinolyl group, a phenanthryl group, a triphenylenyl group, a pyrenyl group, a chrycenyl group, a naphthacenyl group, and a preadenyl group.

  The hydrogen atom of the linear or branched alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms may be further substituted with another substituent.

  Examples of such substituents include halogens such as fluorine, chlorine, bromine and iodine, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p-tolyloxy group, p-bromophenoxy group, Aryloxy groups such as 2,4,6-tribromophenoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, phenoxycarbonyl group, acetoxy group, propionyloxy group, benzoyloxy group Acyloxy group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, phenylsulfuric group Nyl group, arylsulfanyl group such as p-tolylsulfanyl group, alkylamino group such as methylamino group and cyclohexylamino group, dialkylamino group such as dimethylamino group, diethylamino group, morpholino group and piperidino group, phenylamino group, p In addition to arylamino groups such as -tolylamino group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, Examples thereof include a trichloromethyl group, a trimethylsilyl group, a phosphinico group, and a phosphono group.

In addition, when R ¹ , R ² , R ³ , and R ⁴ are a linear or branched alkyl group having 1 to 20 carbon atoms, the hydrogen atom in the alkyl group is a phenyl group or a p-tolyl group. May be substituted with an aryl group such as a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. In addition, when R ¹ , R ² , R ³ , and R ⁴ are aryl groups having 6 to 20 carbon atoms, the hydrogen atom in the aryl group is a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, or the like. It may be substituted with an alkyl group.

Examples of the organic group having a reactive double bond used for R ¹ , R ² , R ³ , and R ⁴ in the chemical formula (1) include, for example, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, (Meta) such as allylcarbonyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, (meth) acryloyl polyoxyethylene group, (meth) acryloyl polyoxypropylene group, (meth) acryloyl polyoxybutylene group ) Acryloyl polyoxyalkylene group (preferably having 1 to 10 oxyalkylene groups), (meth) acryloylalkylene group (preferably having 1 to 12 carbon atoms in the alkylene group), and the like. Preferably, it is at least one selected from the group consisting of vinyl group, allyl group, acryloyl group, methacryloyl group, (meth) acryloyloxyethyl group, and (meth) acryloyloxypropyl group.

In addition, among R ¹ , R ² , R ³ , and R ^{4 in} the chemical formula (1), at least one is an organic group having a reactive double bond, preferably R ¹ and R ⁴ At least one is an organic group having a reactive double bond, and R ² and R ³ are substituents other than the organic group having a reactive double bond.

More preferably, R ¹ and R ⁴ in the chemical formula (1) are organic groups having a reactive double bond, and R ² and R ³ are substituents other than the organic group having a reactive double bond. . In this case, R ¹ and R ⁴ may be the same organic group or different organic groups, and R ² and R ³ may be the same substituent or different substituents. May be.

In the chemical formula (1), R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and preferably R ⁵ and R ⁶ are a methyl group.

  As an example of a C2-C4 alkylene group used by A in the said Chemical formula (1), an ethylene group, n-propylene group, an isopropylene group, n-butylene group, a tert-butylene group etc. are mentioned, for example. It is done.

  M and n in the chemical formula (1) are each independently an integer of 1 to 15, preferably each independently an integer of 1 to 3.

  In the chemical formula (1), a, b, c, and d are each independently 0 or 1.

  Examples of the halogen atom used for X in the chemical formula (1) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a bromine atom.

  E and f in the chemical formula (1) are each independently an integer of 0 to 4, and preferably 2 independently.

  P in the chemical formula (1) is an integer of 1 to 5, preferably 1 or 2.

  As a more preferable compound of the phosphoric ester compound, a compound represented by the following chemical formula (2) or (3) can be given.

[Method for producing phosphate ester compound]
The manufacturing method in particular of the phosphate ester compound of this invention is not restrict | limited, It can manufacture by combining a conventionally well-known method suitably, For example, the method of using phosphorus oxyhalide as a raw material is mentioned.

  As a more specific example, a method for producing a phosphate ester compound represented by the above chemical formula (2) is shown (see the following reaction formulas (1) to (4)).

  First, tetrabromobisphenol A and ethylene carbonate are reacted in the presence of potassium iodide (step 1, hydroxyethylation). This step is a step of introducing an alkylene group represented by A in the chemical formula (1).

  Depending on the structure of the final product, other compounds can be used instead of the raw materials tetrabromobisphenol A and ethylene carbonate.

  Examples of other compounds used instead of tetrabromobisphenol A include bisphenol A, bisphenol E, bisphenol F, and the like. Examples of other compounds used in place of ethylene carbonate include propylene carbonate and butylene carbonate. Furthermore, when synthesizing a compound in which m and n in chemical formula (1) are 2 or more, a known synthesis method using ethylene oxide, propylene oxide, butylene oxide or the like together with an alkali catalyst can be employed.

  Next, phosphorus oxyhalide (phosphorus oxychloride) is reacted with the compound obtained in the above step 1 in the presence of a hydrogen halide scavenger, preferably at a temperature of 0 ° C. or less (step 2). Examples of the hydrogen halide scavenger include aliphatic tertiary amines such as triethylamine and tributylamine, and aromatic tertiary amines such as pyridine, quinoline and lutidine.

  In step 2, phosphorus oxychloride is used as the phosphorus oxyhalide, but phosphorus oxybromide or the like can also be used. However, phosphorus oxychloride is preferred from the viewpoint of availability and cost.

  In Step 2, a Lewis acid catalyst may be used to promote the reaction. Examples of Lewis acid catalysts include magnesium chloride, aluminum chloride, zinc chloride, titanium tetrachloride, boron trifluoride and the like.

  Next, the compound obtained in Step 2 is reacted with the compound having a reactive double bond (2-hydroxypropyl acrylate) in the presence of a hydrogen halide scavenger (Step 3). The reaction time and reaction temperature may be appropriately selected depending on the compound to be used, but are usually reacted at a temperature of 0 to 50 ° C. for 2 to 6 hours.

  Depending on the structure of the desired final product, other compounds having reactive double bonds can be used instead of 2-hydroxypropyl acrylate. Examples of the compound having a reactive double bond other than 2-hydroxypropyl acrylate used in Step 3 include 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl acrylate (2-HEA), 2 -Hydroxyethyl methacrylate (2-HEMA) etc. are mentioned.

  The example of the hydrogen halide scavenger used in step 3 is the same as described above, and thus the description thereof is omitted here.

  Finally, the compound obtained in Step 3 is reacted with 1-propanol in the presence of a hydrogen halide scavenger to obtain the target compound represented by the above chemical formula (2) (Step 4). The reaction time and reaction temperature may be appropriately selected depending on the compound to be used, but are usually reacted at a temperature of 50 to 100 ° C. for 3 to 10 hours.

  Other compounds can be used in place of 1-propanol, depending on the desired final product structure. Examples of compounds other than 1-propanol used in Step 4 include ethylene glycol mono (2,4,6-tribromophenyl) ether, ethanol, 2-ethylhexanol, 4-bromophenol and the like. .

  An example of the hydrogen halide scavenger used in step 4 is the same as described above, and thus the description thereof is omitted here.

  In addition, reaction of the said process 1-4 may be advanced, isolating and refine | purifying the reaction product in each process, or it may carry out a synthesis reaction to the final target compound, without performing isolation and production | generation. Good.

In the above steps 1 to 4, an organic solvent can be used. Specific examples of the organic solvent that can be used include, for example, aliphatic hydrocarbons such as n-hexane and n-heptane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, and cyclohexanone,
Ethers such as diethyl ether, methyl-t-butyl ether, tetrahydrofuran, dioxane, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3-methoxybutyl And esters such as methyl propionate, ethyl propionate, diethyl carbonate and dimethyl carbonate, and aromatic hydrocarbons such as benzene, toluene and xylene. These organic solvents may be used alone or in admixture of two or more.

  The phosphate ester compound of the present invention can be used as a flame retardant for various resins. That is, this invention provides the flame retardant containing the phosphate ester compound of this invention.

  In addition to the phosphoric ester compound of the present invention, the flame retardant of the present invention may contain other components as necessary. Examples of other components include flame retardant aids.

  Examples of the flame retardant aid include, for example, non-condensed or condensed phosphoric acid such as red phosphorus, phosphoric acid, phosphorous acid and the like, amine salts or metal salts, inorganic phosphorus-containing compounds such as boron phosphate, triazine or triazole compounds, Its salts [metal salts, (poly) phosphates, sulfates], urea compounds, nitrogen-containing compounds such as (poly) phosphate amides, organic sulfonic acids [alkane sulfonic acids, perfluoroalkane sulfonic acids, arene sulfonic acids] Or sulfur-containing compounds such as metal salts, sulfonated polymers, organic sulfonic acid amides or salts thereof [ammonium salts, metal salts], silicone compounds such as resins, elastomers and oils containing (poly) organosiloxane, zeolites, etc. Silicon-containing compounds, metal salts of inorganic acids, metal oxides, metal hydroxides, metal sulfides, etc. Inorganic metal compounds. These flame retardant aids can be used alone or in combination of two or more.

  Examples of the various resins include, for example, polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene and ABS (acrylonitrile-butadiene-styrene copolymer) resin, saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, Thermoplastic resins such as vinyl resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyamide resin, polycarbonate resin, acrylic resin, fluororesin, thermoplastic polyimide resin, polyetheretherketone resin, polyamideimide resin, polyethersulfone resin, polysulfone resin Epoxy resin, phenol resin, urea resin, melamine resin, polyurethane resin, unsaturated polyester resin, allyl resin, polyimide resin, alkyl Thermosetting resins such as a resin: or include these polymer blends Hinto.

  In addition, the phosphoric ester compound and the flame retardant of the present invention can be used by applying to the surface of various substrates and curing with ultraviolet rays or the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by the following Example.

(Synthesis Example: Synthesis of Hydroxyethyl Etherified Tetrabromobisphenol A (Compound 1))
543 g (1 mol) of tetrabromobisphenol A, 185 g (2.1 mol) of ethylene carbonate, and 2 g of potassium iodide were charged into a 1 L round bottom glass flask equipped with a mechanical stirrer, an N ₂ blow tube, and a condenser. When the nitrogen-substituted system was heated to 80 to 120 ° C. to start the reaction, the generation of CO ₂ was confirmed. Further, the reaction was continued at 150 to 180 ° C., and when no CO ₂ was generated, the composition was confirmed by gas chromatography, and it was confirmed that the reaction was completed.

  The reaction system was cooled, and the obtained off-white crystals were recrystallized and purified with a mixed solvent of toluene and ethanol to obtain the desired product in a yield of 82% (purity 99.0%).

Example 1
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : n-propyl group, R ⁵ and R ⁶ : methyl group, A: ethylene group, m and n: 1, Synthesis of a compound (compound represented by the above chemical formula (2)) in which a to d: 1, X: Br, e and f: 2, p: 1.
In a 3 L reaction vessel equipped with a mechanical stirrer, N ₂ blow tube, and condenser, 316 g (0.5 mol) of Compound 1 and 153 g (1.0 mol) of phosphorus oxychloride were dissolved in 1000 g of tetrahydrofuran, and −10 ° C. After cooling to 87 g (1.1 mol) of pyridine was added dropwise so that the reaction temperature did not exceed 0 ° C.

  Further, a mixed liquid of 130 g (1 mol) of hydroxypropyl acrylate and 87 g (1.1 mol) of pyridine was dropped so that the liquid temperature did not exceed 5 ° C., and reacted at 25 ° C. for 2 hours. 3 mol) of 1-propanol and 237 g (3 mol) of pyridine were added and reacted at 50 ° C. for 4 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature, and the organic layer was further washed twice with water after stationary separation. Under reduced pressure at 70 to 80 ° C., the solvent and low-boiling impurities such as 1-propanol were removed to obtain a slightly yellow viscous liquid. The yield was 88%. CDCl ₃ was dissolved in (deuterochloroform) in ^confirmed the structure in 1 H-NMR (chemical formula (4) and refer to Table 1). In addition, the following chemical formula (4) is a chemical formula for indicating assignment of ¹ H-NMR, and the structure of the compound is the same as the above chemical formula (2).

(Example 2)
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : 2,4,6-tribromophenoxyethyl group, R ⁵ and R ⁶ : methyl group, A: ethylene group , M and n: 1, a to d: 1, X: Br, e and f: 2, p: 1, compound (compound represented by the above chemical formula (3))]
In a 3 L reaction vessel equipped with a mechanical stirrer, N ₂ blow tube and condenser, 316 g (0.5 mol) of Compound 1 and 153 g (1.0 mol) of phosphorus oxychloride were dissolved in 1000 g of tetrahydrofuran, and −10 After cooling to 0 ° C., 87 g (1.1 mol) of pyridine was added dropwise so that the reaction temperature did not exceed 0 ° C.

  Further, a mixed solution of 130 g (1 mol) of hydroxypropyl acrylate and 158 g (2 mol) of pyridine was dropped so that the liquid temperature did not exceed 5 ° C., and reacted at 25 ° C. for 2 hours, and then 375 g (1 mol). Of ethylene glycol mono (2,4,6-tribromophenyl) ether and 158 g (2 mol) of pyridine were added and reacted at 50 ° C. for 12 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature, and the organic layer was further washed twice with water after stationary separation. The solvent and low boiling point impurities were removed under reduced pressure at 70 to 80 ° C. to obtain a slightly yellow viscous liquid. The yield was 75%. CDCl ₃ was dissolved in (deuterochloroform) in ^confirmed the structure in 1 H-NMR (chemical formula (5) and Table 2). In addition, the following chemical formula (5) is a chemical formula for indicating assignment of ¹ H-NMR, and the structure of the compound is the same as the above chemical formula (3).

(Example 3)
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : n-propyl group, R ⁵ and R ⁶ : methyl group, A: isopropylene group, m and n: 3 , A to d: 1, e and f: 0, p: 1, a compound (compound represented by the following chemical formula (6))]
288 g (0.5 mol) of bisphenol A / propylene oxide 6 mol adduct, 460 g (3.0 mol) of phosphorus oxychloride, and 1.8 g of magnesium chloride as a catalyst were charged into a reaction vessel equipped with a condenser. The temperature of the condenser was controlled at 0 ° C. In order to release the generated hydrogen chloride gas outside the system, the tip of the condenser was connected to a container containing a neutralizing agent.

  The reaction started at about 65 ° C. and reacted at 100 to 110 ° C. for 5 hours, and then unreacted phosphorus oxychloride was recovered over 2 hours under a reduced pressure of 4.0 to 5.3 kPa (30 to 40 Torr). .

  After cooling, the product was dissolved in 1000 g of tetrahydrofuran, and a mixture of 130 g (1 mol) of hydroxypropyl acrylate and 87 g (1.1 mol) of pyridine was added dropwise so that the liquid temperature did not exceed 5 ° C. The reaction was carried out at 2 ° C for 2 hours. Thereafter, 180 g (3 mol) of 1-propanol and 237 g (3 mol) of pyridine were added and reacted at 50 ° C. for 4 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature (25 ° C.), and after standing and separated, the organic layer was further washed twice with water. The solvent and the low boiling point composition such as 1-propanol were removed under reduced pressure at a temperature of 70 to 80 ° C. to obtain a slightly yellow viscous liquid. The yield was 82%. CDCl ₃ was dissolved in (deuterochloroform) in ^confirmed the structure in 1 H-NMR (chemical formula (6) and Table 3).

Example 4
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : p-bromophenyl group, R ⁵ and R ⁶ : methyl group, A: ethylene group, m and n: 1 , A to d: 1, e and f: 2, X: Br, p: 1, a compound (compound represented by the following chemical formula (7))]
In a 3 L reaction vessel equipped with a mechanical stirrer, N ₂ blow tube and condenser, 316 g (0.5 mol) of Compound 1 and 153 g (1.0 mol) of phosphorus oxychloride were dissolved in 1000 g of tetrahydrofuran, and −10 After cooling to 0 ° C., 87 g (1.1 mol) of pyridine was added dropwise so that the reaction temperature did not exceed 0 ° C.

  Further, a mixed solution of 130 g (1 mol) of hydroxypropyl acrylate and 87 g (1.1 mol) of pyridine was dropped so that the liquid temperature did not exceed 5 ° C., and reacted at 25 ° C. for 2 hours, and then 173 g ( 1 mol) of p-bromophenol and 158 g (2 mol) of pyridine were added and reacted at 50 ° C. for 12 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature, and the organic layer was further washed twice with water after stationary separation. The solvent and low boiling point impurities were removed under reduced pressure at 70 to 80 ° C. to obtain a slightly yellow viscous liquid. The yield was 75%. CDCl ₃ was dissolved in ^{(deuterochloroform)} wherein the structure was confirmed by 1 H-NMR (chemical formula (7) and Table 4).

(Comparative Example 1)
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : n-propyl group, R ⁵ and R ⁶ : methyl group, m and n: 0, a to d: 1 , E, and f: 0, p: 1, a compound (compound represented by the following chemical formula (7))]
114 g (0.5 mol) of bisphenol A, 460 g (3.0 mol) of phosphorus oxychloride, and 1.8 g of magnesium chloride as a catalyst were charged into a reaction vessel equipped with a condenser. The temperature of the condenser was controlled at 0 ° C. In order to release the generated hydrogen chloride gas outside the system, the tip of the condenser was connected to a container containing a neutralizing agent.

  The reaction started at about 65 ° C. and reacted at 100 to 110 ° C. for 5 hours, and then unreacted phosphorus oxychloride was recovered over 2 hours under a reduced pressure of 4.0 to 5.3 kPa (30 to 40 Torr). .

  After cooling, the product was dissolved in 1000 g of tetrahydrofuran, and a mixture of 130 g (1 mol) of hydroxypropyl acrylate and 87 g (1.1 mol) of pyridine was added dropwise so that the liquid temperature did not exceed 5 ° C. The reaction was carried out at 2 ° C for 2 hours. Thereafter, 180 g (3 mol) of 1-propanol and 237 g (3 mol) of pyridine were added and reacted at 50 ° C. for 4 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature (25 ° C.), and after standing and separated, the organic layer was further washed twice with water. The solvent and the low boiling point composition such as 1-propanol were removed under reduced pressure at a temperature of 70 to 80 ° C. to obtain a slightly yellow viscous liquid. The yield was 82%. CDCl ₃ was dissolved in (deuterochloroform) in ^confirmed the structure in 1 H-NMR (chemical formula (8) and Table 5).

(Comparative Example 2)
[In the above chemical formula (1), R ¹ and R ⁴ : acryloyloxypropyl group, R ² and R ³ : n-propyl group, R ⁵ and R ⁶ : methyl group, m and n: 0, a to d: 1 , X: Br, e and f: 2, p: 1, Synthesis of Compound (Compound Represented by Chemical Formula (8) below)]
In a 3 L reaction vessel equipped with a mechanical stirrer, N ₂ blow tube and condenser, 272 g (0.5 mol) of tetrabromobisphenol A and 153 g (1.0 mol) of phosphorus oxychloride were dissolved in 1000 g of tetrahydrofuran, After cooling to −10 ° C., 87 g (1.1 mol) of pyridine was added dropwise so that the reaction temperature did not exceed 0 ° C.

  Further, a mixed liquid of 130 g (1 mol) of hydroxypropyl acrylate and 87 g (1.1 mol) of pyridine was dropped so that the liquid temperature did not exceed 5 ° C., and reacted at 25 ° C. for 2 hours. 3 mol) of 1-propanol and 237 g (3 mol) of pyridine were added and reacted at 50 ° C. for 4 hours.

The synthetic solution was diluted with toluene, neutralized with an aqueous hydrochloric acid solution corresponding to an excess of pyridine at room temperature, and the organic layer was further washed twice with water after stationary separation. The solvent and low boiling point impurities were removed under reduced pressure at 70 to 80 ° C. to obtain a slightly yellow viscous liquid. The yield was 73%. CDCl ₃ was dissolved in (deuterochloroform) in ^confirmed the structure in 1 H-NMR (chemical formula (9) and Table 6).

<Evaluation>
The component composition shown in Table 7 below (the unit in Table 7 is parts by mass) was premixed and then kneaded with a three-roll mill to obtain an ultraviolet curable resin composition. The following evaluation was performed about the obtained composition.

(1) Flame retardance Each ultraviolet curable resin composition was applied to a flame retardant substrate RO-67G (0.2 mmt material) manufactured by Hitachi Chemical Co., Ltd. by screen printing on each side by 15 μm, and output was 80 W / cm. UV-cured with No. ³ high-pressure mercury lamp. The test piece was measured for combustion time according to the UL94 combustion test and evaluated according to the following criteria.

A: UL V-0 equivalent (total test time is 50 seconds or less when 5 test pieces are ignited twice each)
○: Equivalent to UL V-1 (total burning time when 5 test pieces are ignited twice each 50 to 250 seconds)
X: No self-extinguishing (total burning time when igniting 5 test pieces twice each is 250 seconds or more)
(2) Flexibility evaluation A cured film prepared on a polycarbonate substrate using each ultraviolet curable resin composition was bent and observed at 180 ° and evaluated according to the following criteria.

○: No crack was confirmed on the film surface ×: The film surface was cracked (3) Compatibility When each ultraviolet curable resin composition was prepared, it was visually confirmed whether or not it was uniformly dissolved.

  The evaluation results are shown in Table 7 below.

  As is apparent from the results in Table 7 above, the ultraviolet curable resin composition containing the phosphate ester compound of the present invention is excellent in flame retardancy, flexibility, and compatibility.

  In Formulation 7, since the phosphate ester compound of Comparative Example 2 was not compatible with the monomer mixture, a resin composition was not obtained, and flame retardancy and flexibility could not be evaluated.

Claims (3)

Phosphate ester compound represented by the following chemical formula (1):

In the chemical formula (1),
R ¹ , R ² , R ³ , and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or non-substituted group. A substituted aryl group having 6 to 20 carbon atoms or an organic group having a reactive double bond, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ has a reactive double bond An organic group,
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group,
A is an alkylene group having 2 to 4 carbon atoms,
m and n are each independently an integer of 1 to 15,
a, b, c, and d are each independently 0 or 1,
X is a halogen atom,
e and f are each independently an integer of 0 to 4,
p is an integer of 1-5.   The organic group having a reactive double bond is at least one selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a (meth) acryloyloxyethyl group, and a (meth) acryloyloxypropyl group. The phosphate ester compound according to claim 1, which is an organic group of   A flame retardant comprising the phosphate ester compound according to claim 1.