Flame retardant compound, and flame retardant resin composition and flame retardant product each using same

Abstract

The present invention relates to a flame retardant compound with a novel structure exhibiting excellent flame retardant properties and improved mechanical properties, and to a flame retardant resin composition and a flame retardant product each using same.

Description

Flame retardant compound and flame retardant resin composition using the same, flame retardant product

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2024-0011859, filed January 25, 2024, the entire disclosure of which is incorporated herein by reference.

[0003] The present invention relates to a flame retardant compound, a flame retardant resin composition using the same, and a flame retardant product. More specifically, the present invention relates to a flame retardant compound capable of improving the flame retardant properties and mechanical properties of a polymer resin, and a flame retardant resin composition using the same, and a flame retardant product.

[0004] Resins used in electrical / electronic products and office equipment must meet flame retardant standards to ensure the safety of electrical / electronic products against fire.

[0005] There are methods for imparting the above flame retardancy, such as a method of polymerizing by including a flame retardant monomer and a method of mixing a flame retardant or flame retardant aid into the manufactured resin, and the flame retardants include halogen-based flame retardants and non-halogen-based flame retardants such as phosphorus-based, nitrogen-based, and hydroxide-based, and the flame retardant aids include antimony-based compounds, silicone-based compounds, and zinc-based compounds.

[0006] The above halogenated flame retardants are the most common because they have higher flame retardancy efficiency than the non-halogenated flame retardants and can maintain the mechanical properties of the resin, and among them, brominated flame retardants are particularly effective. However, when brominated flame retardants are added to the resin during processing, the high temperatures and pressures generated during processing reduce thermal stability, causing decomposition, resulting in the generation of corrosive and toxic gases, which can have a negative impact on the work environment and human health.

[0007] One way to circumvent the above problems is to use non-halogenated flame retardants, and among these, the method using non-halogenated flame retardant compounds is widely used. However, non-halogenated flame retardant compounds have lower flame retardancy efficiency than halogenated flame retardants, so they require excessive amounts of non-halogenated flame retardant compounds. In addition, due to the principle of phosphorus-based flame retardant systems, thermoplastic resin compositions that do not generate char have difficulty fully demonstrating flame retardancy.

[0008] Accordingly, there is a need for the development of a non-halogenated flame retardant suitable for increasing the flame retardancy of polymer resins.

[0009] The present invention provides a flame retardant compound capable of improving the flame retardant properties and mechanical properties of a polymer resin.

[0010] In addition, the present invention provides a flame retardant resin composition including the flame retardant compound.

[0011] In addition, the present invention provides a flame retardant product including the flame retardant resin composition.

[0012] In this specification, a flame retardant compound represented by the following chemical formula 1 is provided.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] R1 is substituted or unsubstituted linear or branched alkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, O, S or NR7,

[0017] R2, R5 and R6 are the same or different from each other and are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,

[0018] R3 and R4 are the same or different from each other, and each independently represents a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkylaryl group,

[0019] R7 is hydrogen or a substituted or unsubstituted alkyl group,

[0020] M is at least one selected from the group consisting of metal and ammonium ions,

[0021] n, m, x and y are equal to or different from each other and are each independently an integer from 1 to 5.

[0022] The present specification also provides a flame retardant resin composition comprising the flame retardant compound; and a binder resin.

[0023] The present specification also provides a flame retardant product including the flame retardant resin composition.

[0024] Hereinafter, flame retardant compounds according to specific embodiments of the invention and flame retardant resin compositions and flame retardant products using the same will be described in more detail.

[0025]

[0026] In this specification, when a part is said to "include" a certain component, this means that it may include other components, but not to the exclusion of other components, unless specifically stated otherwise.

[0027] In this specification, examples of substituents are described below, but are not limited thereto.

[0028] In this specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in a compound, and the position of substitution is not limited as long as it is a position where a hydrogen atom is substituted, i.e., a position where a substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same or different from each other.

[0029] The term "substituted or unsubstituted" as used herein means a group that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; an amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, the "substituent linked with two or more substituents" may be a biphenyl group. That is, the biphenyl group can be an aryl group or can be interpreted as a substituent in which two phenyl groups are connected.

[0030] In the present specification, the alkyl group may be straight-chain (linear) or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms in the branched-chain alkyl group is 3 to 20. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexetylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, Examples thereof include, but are not limited to, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl. The alkyl group may be substituted or unsubstituted, and examples of the substituent when substituted are as described above.

[0031] In the present specification, the aryl group is not particularly limited, but is preferably one having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but is not limited thereto. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0032] In the present specification, a heteroaryl group includes one or more non-carbon atoms or heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of heterocyclic groups include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, Examples thereof include, but are not limited to, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, an aziridyl group, an azaindolyl group, an isoindolyl group, an indazolyl group, a purine group, a pteridyl group, a beta-carbolyl group, a naphthyridine group, a tert-pyridyl group, a phenazinyl group, an imidazopyridyl group, a pyropyridyl group, an azepine group, a pyrazolyl group, and a dibenzofuranyl group. The heteroaryl group may be substituted or unsubstituted, and examples of the substituent when substituted are as described above.

[0033]

[0034] According to one embodiment of the invention, a flame retardant compound represented by the following chemical formula 1 can be provided.

[0035] [Chemical Formula 1]

[0036]

[0037] In the above chemical formula 1,

[0038] R1 is a substituted or unsubstituted linear or branched alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, O, S or NR7,

[0039] R2, R5 and R6 are the same or different from each other and are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,

[0040] R3 and R4 are the same or different and are each independently a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkylaryl group,

[0041] R7 is hydrogen or a substituted or unsubstituted alkyl group,

[0042] M is at least one selected from the group consisting of metal and ammonium ions,

[0043] n, m, x and y are equal to or different from each other and are each independently an integer from 1 to 5.

[0044]

[0045] The present inventors have experimentally confirmed that, when a compound obtained by a coordination bond between two types of phosphorus ligands of a specific structure and a metal element, as represented by the above chemical formula 1, is applied as a flame retardant, the flame retardant characteristics and mechanical properties of a polymer resin (i.e., a binder resin) included in a flame retardant resin composition can be significantly improved, and thus the invention has been completed. In addition, the flame retardant compound represented by the above chemical formula 1 can not only increase the flame retardant characteristics of a thermoplastic resin composition when the same amount is applied compared to a conventional halogen-based flame retardant, but also exhibit sufficient flame retardancy even when a smaller amount is used compared to the existing flame retardants, thereby more effectively providing a flame retardant product with excellent flame retardancy.

[0046]

[0047] Specifically, a flame retardant compound for improving the flame retardant properties of a polymer resin may include two types of ligand repeating units represented by the above chemical formula 1.

[0048] In the above chemical formula 1, the alkylene group, arylene group and heteroarylene group defined in R1 may each be a divalent organic group derived from a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 2 to 60 carbon atoms. Preferably, the alkylene, arylene and heteroarylene groups of R1 are each independently deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; an amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; It may be substituted with one or more substituents selected from the group consisting of an arsenic group; an alkylaryl group; an arylphosphine group; and a heteroaryl group. Specifically, the alkylene, arylene, and heteroarylene groups of R2 to R5 may each be independently substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; an amide group; a carboxyl group; an alkyl group; an aryl group; and a heteroaryl group.

[0049] In the above chemical formula 1, the alkyl group, aryl group and heteroaryl group defined in R2 to R6 may each be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 2 to 60 carbon atoms. Preferably, the alkyl, aryl and heteroaryl groups of R2 to R6 are each independently deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; an amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; Arylphosphine group; and heteroaryl group may be substituted with one or more substituents selected from the group consisting of. Specifically, the alkyl, aryl and heteroaryl groups of R2 to R6 may each be independently substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; an amide group; a carboxyl group; an alkyl group; an aryl group; and a heteroaryl group.

[0050] In addition, according to a preferred embodiment, in the chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene group, O or NR7, R2, R5 and R6 are the same as or different from each other and are each independently a substituted or unsubstituted linear or branched alkyl group or a substituted or unsubstituted aryl group, R3 and R4 are the same as or different from each other and are each independently a substituted or unsubstituted linear or branched alkyl group or a substituted or unsubstituted aryl group, and R7 may be hydrogen or a substituted or unsubstituted alkyl group.

[0051] Specifically, according to one embodiment of the invention, in the chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, O, or NR7, R2, R5, and R6 are the same as or different from each other, and each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R3 and R4 are the same as or different from each other, and each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. In addition, R7 may be hydrogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.

[0052] More specifically, R1 is an unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms or O, and R2 to R6 are the same as or different from each other and can each independently be an unsubstituted linear alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 20 carbon atoms.

[0053] In cases like the above, the phosphorus flame retardant compound is x - When forming a coordination bond between M metals with ligands and y-ligands, x composed of substituents of chemical formula 1 - By including a ligand, a flame retardant composition including the ligand can maintain particularly excellent flame retardant properties and also secure excellent mechanical properties.

[0054] In addition, in the above chemical formula 1, the M may be at least one selected from the group consisting of metals and ammonium ions. More specifically, the M may be at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and ammonium ions. The M may be at least one selected from the group consisting of Al, Zn, Mg, Ca, and ammonium ions.

[0055] In addition, in the above chemical formula 1, n, m, x and y are the same as or different from each other, and are each independently an integer from 1 to 5.

[0056] In addition, in the chemical formula 1, (nx+my)+ means the cation valence of the metal element M. Specifically, nx means a value obtained by multiplying n and x, my means a value obtained by multiplying m and y, and nx+my can be 1 to 10.

[0057]

[0058] Meanwhile, the flame retardant compound represented by the above chemical formula 1 may be a coordination bond between a ligand including at least one selected from the group consisting of a first ligand represented by the following chemical formula 2 and at least one selected from the group consisting of a second ligand represented by the following chemical formula 3, and a central metal element M. That is, a coordination bond between a ligand including a total of n first ligands represented by the following chemical formula 2 and a total of m second ligands represented by the following chemical formula 3, and a central metal element M may be the flame retardant compound represented by the above chemical formula 1. According to a preferred example, the flame retardant compound of the above chemical formula 1 may be a coordination bond between a ligand including a first ligand represented by the following chemical formula 2 and a second ligand represented by the following chemical formula 3, wherein n and m are 1, and a central metal element M.

[0059] [Chemical Formula 2]

[0060]

[0061] [Chemical Formula 3]

[0062]

[0063] In the above chemical formulas 2 to 3, the contents of R1 to R5, x, y, n, and m are the same as the above definitions.

[0064] Specifically, the first ligand represented by the above chemical formula 2 is not particularly limited in specific examples, but for example, the compound represented by the above chemical formula 1 may include any one of the first ligands selected from the following structural formulas.

[0065]

[0066] In addition, the second ligand represented by the above chemical formula 3 is not particularly limited in specific examples, but for example, the compound represented by the above chemical formula 1 may include any one of the second ligands selected from the structural formulas below.

[0067]

[0068]

[0069] Meanwhile, the flame retardant compound represented by the above chemical formula 1 is not particularly limited in specific examples, but may include, for example, any one selected from compounds having the following structural formula.

[0070]

[0071]

[0072] Examples of a method for producing a flame retardant compound represented by the above chemical formula 1 are not particularly limited, but may include, for example, a process of reacting a metal salt and a ligand precursor compound in the presence of a base.

[0073] An example of the above metal salt is an aluminum salt such as Al2(SO4)3.

[0074] The above ligand precursor compound is a compound that reacts with a base to convert into a ligand compound in an anionic form, and may be a phosphoric acid compound or a carboxylic acid compound. The phosphoric acid compound may include phosphoric acid, phosphorous acid, hypophosphorous acid, or a derivative compound thereof. The carboxylic acid compound may include a carboxylic acid or a derivative compound thereof.

[0075] Examples of the above bases are not particularly limited, and include LiOH, NaOH, TEA, Cs2CO3, or mixtures thereof.

[0076] Examples of reaction conditions between a metal salt and a ligand precursor compound in the presence of the above base are also not particularly limited, and reaction conditions between a metal salt and a ligand precursor compound known in the art can be applied without limitation.

[0077]

[0078] Meanwhile, according to another embodiment of the invention, a flame retardant resin composition comprising the flame retardant compound of the above embodiment; and a binder resin; can be provided.

[0079] The content regarding the above flame retardant compound includes the content described above with respect to the above embodiment.

[0080] The above binder resin can be applied without limitation to a variety of conventionally known thermoplastic resins, thermosetting resins, or their single, blended, or copolymerized forms, and specific examples include polyester resins, polyamide resins, polyolefin resins, polyurethane resins, polyimide resins, epoxy resins, phenol resins, and polyphenylene sulfide resins, or mixtures thereof.

[0081] Based on the total weight of the solid content in the flame retardant resin composition, the content of the flame retardant compound may be 1 wt% to 30 wt%, or 5 wt% to 30 wt%, or 10 wt% to 30 wt%, or 15 wt% to 30 wt%, or 15 wt% to 20 wt%. In addition, the content of the binder resin may be 70 wt% to 99 wt%, or 70 wt% to 95 wt%, or 70 wt% to 90 wt%, or 70 wt% to 85 wt%, or 80 wt% to 85 wt%.

[0082] The total weight of the above solids refers to the sum of the total weights of the components in the resin composition, excluding the solvent. The solids content and the weight percent based on the solids content of each component can be measured using general analytical methods used in the art, such as liquid chromatography or gas chromatography.

[0083] The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2-ethoxy propanol, It may be at least one selected from the group consisting of 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, but is not limited thereto.

[0084] In addition, the flame retardant resin composition may further include other additives. The content of the other additives is 0.01 wt% to 20 wt% based on the total weight of the solid content in the flame retardant resin composition.

[0085] The types, methods, and timings of the above-mentioned other additives are not particularly limited, and various known contents can be applied without limitation. Specific examples of the additives include impact modifiers, antioxidants, compatibilizers, hydrolysis stabilizers, ultraviolet stabilizers, heat stabilizers, color additives, fixatives, flame retardants, fiber reinforcing materials, inorganic fillers, nucleating agents, lubricants, release agents, coloring agents, hydrolysis stabilizers, viscosity enhancers, optical whitening agents, chain extenders, pigments, dyes, antistatic agents, or mixtures of two or more thereof.

[0086] Meanwhile, the flame retardant resin composition may have a flame retardancy of VO or V1 grade measured according to the UL-94 test standard. Examples of specimens for which flame retardancy is measured according to the UL-94 standard are not particularly limited, but for example, the flame retardant resin composition may be mixed with a twin-screw extruder at a temperature of 230°C to 260°C or a temperature of 260°C to 280°C, homogenized polymer strands may be drawn, cooled in a water bath, pelletized, sufficiently dried, and then processed in an injection molding machine at a melting temperature of 240°C to 270°C or a melting temperature of 260°C to 290°C to obtain a specimen having a thickness of 1.6 mm, a width of 12.7 mm, and a length of 127 mm. The above flame retardant resin composition can realize excellent flame retardant properties by satisfying the VO or V1 grade in flame retardancy measured according to the UL-94 test standard, and if the flame retardancy measured according to the UL-94 test standard increases to the V2 grade or higher, the flame retardant properties become poor.

[0087] Meanwhile, the flame retardant resin composition has a tensile strength of 425 kgf / cm as measured according to the ASTM D638 method. 2 or 428 kgf / cm 2 or 425 kgf / cm 2 Up to 500 kgf / cm 2 , or 428 kgf / cm 2 Up to 480 kgf / cm 2It can be. The examples of specimens, equipment, and conditions used for the above tensile strength measurement are not particularly limited, and the ASTM D638 method and the conventionally known tensile strength measurement method of resin molded products can be applied without limitation. However, as an example, specifically, using UTM-5566 (Universal Testing Machine, Instron), 5 dumbbell-shaped specimens are manufactured according to the ASTM D638 regulations, and then the tensile strength for each of the 5 specimens is measured at a speed of 50 mm / min, and the result can be expressed as the average value. The flame retardant resin composition has a tensile strength of 425 kgf / cm as measured according to the ASTM D638 method. 2 It can realize excellent tensile properties by satisfying the above, and the tensile strength is 425 kgf / cm. 2 If it falls below this level, the tensile properties become poor.

[0088] Meanwhile, the flame retardant resin composition may have an impact strength of 2.1 kgf·cm / cm or more, or 2.1 kgf·cm / cm to 3.0 kgf·cm / cm, or 2.1 kgf·cm / cm to 2.6 kgf·cm / cm, measured at 23°C according to ASTM D256 (1 / 8 inch, Notched Izod). Examples of specimens, equipment, and conditions used for measuring the impact strength are not particularly limited, and the ASTM D256 method and a conventionally known method for measuring the impact strength of a resin molded product may be applied without limitation. The flame retardant resin composition may have an impact strength of 2.1 kgf·cm / cm or more measured at 23°C according to ASTM D256 (1 / 8 inch, Notched Izod), thereby realizing excellent impact properties. If the impact strength is lowered to less than 2.1 kgf·cm / cm, the impact properties become poor.

[0089]

[0090] Meanwhile, according to another embodiment of the invention, a flame retardant product comprising the flame retardant resin composition of the other embodiment can be provided.

[0091] The content regarding the above flame retardant resin composition includes the content described above regarding the other embodiments.

[0092] The above flame-retardant product may include the flame-retardant resin composition of the other embodiment, or a molded article thereof. The flame-retardant resin composition may be directly coated on the product to form a flame-retardant coating layer, or may be coated on a component of the product and introduced into the product.

[0093] The specific shape and size of the above molded product may vary depending on its intended use, and examples thereof are not particularly limited. Examples of the above molding method are also not limited, and molding methods widely known in the field of molding resin compositions can be applied without limitation. For example, the above molded product can be obtained by molding the flame-retardant resin composition according to its intended use, through various molding methods, such as molding processes such as injection molding, extrusion, extrusion blow molding, injection blow molding, and profile extrusion, and post-processing such as a thermoforming process using the same.

[0094] Examples of the types of the above products are not particularly limited and may include, for example, electrical / electronic products and automobile parts.

[0095] According to the present invention, a novel structural phosphorus flame retardant compound capable of improving the flame retardant properties and mechanical properties of a polymer resin, and a flame retardant resin composition and flame retardant product using the same can be provided.

[0096] The invention is described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

[0097]

[0098] <Manufacturing Examples 1 to 6: Preparation of flame retardant compounds>

[0099] Manufacturing Example 1

[0100] A compound represented by Chemical Formula 1-1 was synthesized through a reaction as shown in [Reaction Scheme 1] below.

[0101] [Reaction Formula 1]

[0102]

[0103] The above L-1 compound and diethylphosphinic acid (M-1 compound) were added as reactants to the reactor at a molar ratio of 1:2, NaOH as a base was dissolved in water at room temperature and stirred, and then Al2(SO4)3 was added as an aluminum salt, the temperature was raised to 100°C, and the mixture was stirred for 12 hours to react.

[0104] The solid was isolated by vacuum filtration using a suction filter and washed with additional water and acetone (twice each) to purify the solid product. The solid product was transferred to a glass bottle, placed in a vacuum oven, and dried overnight to obtain compound 1-1. (Yield: 90%)

[0105] [Chemical Formula 1-1]

[0106]

[0107]

[0108] Manufacturing Example 2

[0109] A compound represented by chemical formula 1-2 was synthesized through a reaction as shown in [Reaction Scheme 2] below.

[0110] [Reaction Formula 2]

[0111]

[0112] A compound represented by Chemical Formula 1-2 was synthesized in the same manner as in Manufacturing Example 1, except that L-2 (molar ratio 1:1) was used instead of L-1 as a reactant. (Yield: 92%)

[0113] [Chemical Formula 1-2]

[0114]

[0115]

[0116] Manufacturing Example 3

[0117] [Reaction Formula 3]

[0118] A compound represented by chemical formula 1-3 was synthesized through a reaction as shown in [Reaction Scheme 3] below.

[0119]

[0120] A compound represented by Chemical Formula 1-3 was synthesized in the same manner as in Manufacturing Example 1, except that L-3 was used instead of L-1 and M-2 was used instead of M-1 (molar ratio 1:1) as the reactants. (Yield: 88%)

[0121] [Chemical Formula 1-3]

[0122]

[0123]

[0124] Manufacturing Example 4

[0125] [Reaction Formula 4]

[0126] A compound represented by chemical formula 1-4 was synthesized through a reaction as shown in [Reaction Scheme 4] below.

[0127]

[0128] A compound represented by Chemical Formula 1-4 was synthesized in the same manner as in Manufacturing Example 1, except that L-4 was used instead of L-1 and M-3 was used instead of M-1 (molar ratio 1:1) as the reactants. (Yield: 91%)

[0129] [Chemical Formula 1-4]

[0130]

[0131]

[0132] Manufacturing Example 5

[0133] [Reaction Formula 5]

[0134]

[0135] A compound represented by Chemical Formula 1-5 was synthesized in the same manner as in Preparation Example 1, except that L-5 (molar ratio 1:2) was used instead of L-1 as a reactant. (Yield: 95%)

[0136] [Chemical Formula 1-5]

[0137]

[0138]

[0139] Manufacturing Example 6

[0140] [Reaction Formula 6]

[0141]

[0142] A compound represented by Chemical Formula 1-6 was synthesized in the same manner as in Preparation Example 1, except that L-6 (molar ratio 2:1) was used instead of L-1 as a reactant. (Yield: 93%)

[0143] [Chemical Formula 1-6]

[0144]

[0145]

[0146] <Comparative Manufacturing Example 1: Manufacturing of Flame Retardant Compound>

[0147] Comparative Manufacturing Example 1

[0148] The following compound A-1 was used as comparative manufacturing example 1.

[0149] [Compound A-1]

[0150]

[0151]

[0152] <Examples 1 to 6: Preparation of flame-retardant resin composition>

[0153] A flame-retardant resin composition was prepared using the compounds of the above chemical formulas 1-1 to 1-6 as a phosphorus flame retardant.

[0154] According to the composition of Table 1 below, 85 wt% of thermoplastic resin and 15 wt% of phosphorus flame retardant based on the total weight of solid content in the flame retardant resin composition were mixed in a mixer for 5 to 20 minutes, then added to an extruder, and melted and extruded under conditions of a cylinder temperature of 240°C and a stirring speed of 200 rpm to produce pellets. The produced pellets were dried at 90°C for one day and then injected at 240°C to produce specimens for measuring physical properties.

[0155] Classification Thermoplastic resin additive (flame retardant) Example 1 Polybutylene terephthalate (PBT) Intrinsic Viscosity (IV): 0.8 to 1.2 dl / g 1-1 Phosphorus-based flame retardant 1 (Manufacturing Example 1) Example 2 1-2 Phosphorus-based flame retardant 2 (Manufacturing Example 2) Example 3 1-3 Phosphorus-based flame retardant 3 (Manufacturing Example 3) Example 4 1-4 Phosphorus-based flame retardant 4 (Manufacturing Example 4) Example 5 1-5 Phosphorus-based flame retardant 5 (Manufacturing Example 5) Example 6 1-6 Phosphorus-based flame retardant 6 (Manufacturing Example 6) Comparative Example 1A-1 Phosphorus-based flame retardant 7 (Comparative Manufacturing Example 1)

[0156]

[0157] <Comparative Example 1: Preparation of Flame-Retardant Resin Composition>

[0158] Comparative Example 1

[0159] A resin composition was manufactured in the same manner as in Example 1, except that Compound A-1 obtained in Comparative Manufacturing Example 1 was used instead of Compound 1-1, a phosphorus flame retardant obtained in Manufacturing Example 1, as shown in Table 1 above.

[0160]

[0161] <Experimental Example: Measurement of Physical Properties of Flame-Retardant Resin Composition>

[0162] The physical properties of the flame-retardant resin compositions obtained in the above examples and comparative examples were measured by the following methods, and the results are shown in Table 3.

[0163]

[0164] 1. Flame retardant properties

[0165] The flame retardant components obtained in the above practical and comparative examples were mixed with polymer pellets and optional additives, and mixed in a twin-screw extruder at a temperature of 230°C to 260°C, or 260°C to 280°C. The homogenized polymer strands were drawn, cooled in a water bath, and then pelletized.

[0166] After sufficient drying, the molding composition was processed in an injection molding machine at a melting temperature of 240°C to 270°C or a melting temperature of 260°C to 290°C to obtain a specimen. Using a specimen with a thickness of 1.6 mm, a width of 12.7 mm, and a length of 127 mm, the flame retardancy was evaluated according to the UL-94 test standard.

[0167] Specifically, after contacting the specimen with a 20 mm high flame for 10 seconds, the specimen's combustion time (t1) was measured and the combustion pattern was recorded. Then, after combustion was completed after the first contact, the specimen was contacted again for 10 seconds, and the specimen's combustion time (t2) and the time until sparks formed (glowing time, t3) were measured and the combustion pattern was recorded. The same procedure was applied to five specimens and then evaluated based on the criteria in Table 2 below.

[0168] Flame retardancy grade V0 V1 V2 Individual burning time (t1 or t2 of individual specimen) 10 seconds or less 30 seconds or less 30 seconds or less Total burning time of 5 specimens (sum of t1 and t2 of 5 specimens) 50 seconds or less 250 seconds or less 250 seconds or less Time for combustion and ignition after secondary contact (sum of t2 and t3 of individual specimens) 30 seconds or less 60 seconds or less 60 seconds or less Whether or not it sheds flammable particles None None None

[0169]

[0170] 2. Other properties besides flame retardancy

[0171] (1) Tensile strength: Measured according to the ASTM D638 method. Specifically, using UTM-5566 (Universal Testing Machine, Instron), five dumbbell-shaped specimens were manufactured according to the ASTM D638 regulations, and the tensile strength of each of the five specimens was measured at a speed of 50 mm / min, and the results were expressed as the average value.

[0172] (2) Izod impact strength at room temperature: Measured at 23 ℃ according to ASTM D256 (1 / 8 inch, Notched Izod).

[0173]

[0174] Experimental example Results Example Additive Flame retardant properties Tensile strength (kgf / cm) 2 ) Impact strength (kgf·cm / cm) UL grade Example 11-1V-01314.0 Example 21-2V-01403.0 Example 31-3V-01453.2 Example 414V-01352.8 Example 51-5V-01413.1 Example 61-6V-01383.5 Comparative example 1A-1V-01302.3

[0175] As shown in Table 3 above, the flame retardant resin compositions obtained in Examples 1 to 6 have x composed of a substituent of Chemical Formula 1 compared to Comparative Example 1. - By including a phosphorus flame retardant compound that is a metal coordination compound containing a ligand, it was confirmed that the flame retardant properties were excellent with a UL rating of VO or V1, and at the same time, both tensile strength and impact strength were high.

[0176] On the other hand, Comparative Example 1 is composed of x as a substituent of Chemical Formula 1. - Even though the UL rating of VO was shown for a general phosphorus flame retardant compound that did not contain a ligand, the tensile strength and impact strength were lower than those of the examples.

Claims

1. A flame retardant compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, O, S or NR7, R2, R5 and R6 are the same or different from each other and are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R3 and R4 are the same or different and are each independently a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkylaryl group, R7 is hydrogen or a substituted or unsubstituted alkyl group, M is at least one selected from the group consisting of metal and ammonium ions, n, m, x and y are equal to or different from each other and are each independently an integer from 1 to 5.

2. In the first paragraph, in the chemical formula 1, The above R1 is a substituted or unsubstituted linear or branched alkylene group, O or NR7, The above R2, R5 and R6 are the same or different from each other, and each independently represents a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group, The above R3 and R4 are the same or different from each other, and each independently represents a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group, A flame retardant compound wherein R7 is hydrogen or a substituted or unsubstituted alkyl group.

3. In the first paragraph, in the chemical formula 1, The above R1 is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, O, or NR7, The above R2, R5 and R6 are the same or different from each other, and each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. A flame retardant compound wherein R3 and R4 are the same or different from each other and each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

4. In paragraph 1, The above M is a flame retardant compound, wherein at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and ammonium ions.

5. In paragraph 4, The above M is a flame retardant compound, wherein at least one member is selected from the group consisting of Al, Zn, Mg, Ca, and ammonium ions.

6. In the first paragraph, the flame retardant compound represented by the chemical formula 1 is a flame retardant compound that is a coordination bond between a ligand and a central metal element M, including at least one selected from the group consisting of a first ligand represented by the following chemical formula 2 and at least one selected from the group consisting of a second ligand represented by the following chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 to 3, the contents of R1 to R6, x, y, n, and m are the same as the definitions in the first paragraph above.

7. In paragraph 1, The flame retardant compound represented by the above chemical formula 1 is a flame retardant compound comprising any one selected from compounds having the following structural formula:

8. A flame retardant resin composition comprising the flame retardant compound of paragraph 1; and a binder resin.

9. In paragraph 8, A flame retardant resin composition, wherein the binder resin comprises polyester or polyamide.

10. In paragraph 8, A flame retardant resin composition, wherein the content of the flame retardant compound is 1 wt% to 30 wt% based on the total weight of the solid content in the flame retardant resin composition.

11. A flame retardant product comprising the flame retardant resin composition of Article 8.

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