Flame retardant compounds and flame retardant resin compositions and flame retardant products using the same

Abstract

This invention relates to a novel flame retardant compound with excellent flame retardant properties and improved mechanical properties, as well as a flame retardant resin composition and flame retardant product using the same.

Description

[Technical Field]

[0001] [Cross-citation with related applications] This application claims priority based on Korean Patent Application No. 10-2024-0011859 dated January 25, 2024, and all content disclosed in the said Korean Patent Application is incorporated herein as part of this specification.

[0002] This invention relates to flame retardant compounds and flame retardant resin compositions and flame retardant products using the same. More specifically, it relates to flame retardant compounds that can improve the flame retardant properties and mechanical properties of polymer resins, and flame retardant resin compositions and flame retardant products using the same. [Background technology]

[0003] Resins used in electrical / electronic products and office equipment must meet flame retardancy standards to ensure the fire resistance of electrical / electronic products.

[0004] Methods for imparting the aforementioned flame retardancy include polymerizing a flame retardant monomer and mixing a flame retardant and a flame retardant aid into the manufactured resin. The flame retardant includes halogen-based flame retardants and non-halogen-based flame retardants such as phosphorus-based, nitrogen-based, and hydroxide-based flame retardants, while the flame retardant aids include antimony compounds, silicon-based compounds, and zinc compounds.

[0005] The halogen-based flame retardants are the most common because they have higher flame retardancy efficiency than the non-halogen-based flame retardants and can maintain the mechanical properties of the resin, with brominated flame retardants being particularly effective. However, when processing resins with brominated flame retardants, the high temperatures and pressures generated during processing reduce thermal stability and cause decomposition, which generates corrosive and toxic gases that have adverse effects on the work environment and human health.

[0006] One way to avoid the aforementioned problems is to use non-halogenated flame retardants, and among these, methods using non-halogenated flame retardant compounds are widely used. However, non-halogenated flame retardant compounds have lower flame retardancy efficiency compared to halogenated flame retardants, which means that an excessive amount of the non-halogenated flame retardant compound must be added. Furthermore, due to the principle of phosphorus-based flame retardant systems, thermoplastic resin compositions that cannot generate char do not exhibit sufficient flame retardancy.

[0007] Therefore, there is a need for the development of non-halogenated flame retardants suitable for increasing the flame retardancy of polymer resins. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] This invention provides a flame retardant compound that can improve the flame retardant properties and mechanical properties of polymer resins.

[0009] Furthermore, the present invention provides a flame-retardant resin composition containing the aforementioned flame-retardant compound.

[0010] Furthermore, the present invention provides a flame-retardant product containing the flame-retardant resin composition. [Means for solving the problem]

[0011] This specification provides a flame retardant compound represented by the following chemical formula 1.

[0012] [Chemical formula 1] [ka]

[0013] In the aforementioned chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene, a substituted or unsubstituted arylene, a substituted or unsubstituted heteroarylene, O, S, or NR7. R2, R5 and R6 are the same as or different from each other, and are each independently hydrogen, a hydroxy 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 as or different from each other, 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 one or more selected from the group consisting of metals and ammonium ions, n, m, x and y are the same as or different from each other, and are each independently an integer of 1 to 5.

[0014] The present specification further provides a flame-retardant resin composition comprising the flame retardant compound; and a binder resin.

[0015] The present specification further provides a flame-retardant article comprising the flame-retardant resin composition.

[0016] Hereinafter, a flame retardant compound according to a specific embodiment of the present invention, a flame-retardant resin composition using the same, and a flame-retardant article will be described in more detail.

[0017] In the present specification, when a portion "comprises" a component, this does not exclude other components unless specifically stated to the contrary, and means that the portion may further comprise other components.

[0018] In the present specification, examples of the substituent are described below, but the substituent is not limited thereto.

[0019] As used herein, the term "substitution" means that another functional group is bonded to a compound in place of a hydrogen atom therein. The position of substitution is not limited as long as it is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted. When two or more substitutions are performed, two or more substituents may be the same or different from each other.

[0020] As used herein, the term "substituted or unsubstituted" means that a group is substituted or unsubstituted 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 carboxy group, a sulfonic acid group, a sulfonamide group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthiooxy group, an arylthiooxy 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, and a heterocyclic group containing one or more of N, O and S atoms, or two or more of the above-exemplified substituents are linked and the resulting group is substituted or unsubstituted. For example, "a substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may also be interpreted as a substituent formed by linking two phenyl groups.

[0021] In this specification, alkyl groups may be linear or branched, and the number of carbon atoms in the linear alkyl group is not particularly limited, but is preferably 1 to 20. The number of carbon atoms in the branched alkyl group is 3 to 20. Specific examples of alkyl groups include, but are not limited to, 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl. The alkyl group may be substituted or unsubstituted, and if substituted, examples of substituents are as described above.

[0022] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. In one embodiment, the aryl group has 6 to 30 carbon atoms. In another embodiment, the aryl group has 6 to 20 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, and terphenyl groups. Examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, phenanthryl, pyrenyl, perilenyl, chrysenyl, and fluorenyl groups. The aryl group may be substituted or unsubstituted, and if substituted, examples of substituents are as described above.

[0023] In this specification, a heteroaryl group contains 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 between 2 and 60, 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, pyridadinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyradinyl group, pyrazinopyradinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, and dibenzothiophene. Examples of heteroaryl groups include, but are not limited to, benzofuranyl, phenanthrolinyl, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, aziridyl, azaindolyl, isoindolyl, indazolyl, purine, pteridine, β-caboryl, naphthyridine, tert-pyridyl, phenazinyl, imidazopyridyl, pyropyridyl, azepine, pyrazolyl, and dibenzofuranyl groups. The heteroaryl group may be substituted or unsubstituted, and examples of substituents are as described above.

[0024] According to one embodiment of the present invention, a flame retardant compound represented by the following chemical formula 1 can be provided.

[0025] [Chemical formula 1] [ka]

[0026] In the aforementioned 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 either identical or different from each other, and each is independently a hydrogen atom, 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 either identical or different from each other, and independently of each other, are 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 one or more selected from the group consisting of metals and ammonium ions. n, m, x, and y are integers between 1 and 5, and are either identical or different from each other, and are independent of each other.

[0027] The inventors of the present invention have confirmed through experiments that when a compound obtained by coordination bonding between two phosphorus-based ligands of a specific structure and a metal element, as represented by the above-mentioned chemical formula 1, is applied as a flame retardant, the flame retardant properties and mechanical properties of the polymer resin (i.e., binder resin) contained in the flame retardant resin composition can be significantly improved, thereby completing the invention. Furthermore, compared to conventional halogen-based flame retardants, the above-mentioned flame retardant compound represented by chemical formula 1 can not only increase the flame retardant properties of thermoplastic resin compositions when the same content is applied, but also exhibits sufficient flame retardancy even when using a smaller content than existing flame retardants, thereby providing flame retardant products with superior flame retardancy more effectively.

[0028] Specifically, a flame retardant compound for improving the flame retardant properties of a polymer resin may contain two ligand repeating units represented by the chemical formula 1 described above.

[0029] 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 group of R1 may each be independently substituted with one or more substituents selected from the group consisting of deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthiooxy group; arylthiooxy group; alkylsulfoxy group; arylsulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; arylphosphine group; and 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, halogen groups, cyano groups, nitro groups, hydroxyl groups, amide groups, carboxyl groups, alkyl groups, aryl groups, and heteroaryl groups.

[0030] In the above chemical formula 1, the alkyl, aryl, and heteroaryl groups defined in R2 to R6 may each be a substituted or unsubstituted C1 to C30 alkyl, C6 to C60 aryl, or C2 to C60 heteroaryl group. Preferably, 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; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthiooxy group; arylthiooxy group; alkylsulfoxy group; arylsulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; arylphosphine group; and heteroaryl group. 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, halogen groups, cyano groups, nitro groups, hydroxyl groups, amide groups, carboxyl groups, alkyl groups, aryl groups, and heteroaryl groups.

[0031] Furthermore, in one preferred embodiment, in the above chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene group, O, or NR7; R2, R5, and R6 are the same or different from each other and are independently a substituted or unsubstituted linear or branched alkyl group or a substituted or unsubstituted aryl group; R3 and R4 are the same or different from each other and are 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.

[0032] Specifically, according to one embodiment of the present invention, in the above 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 or different from each other, and each is independently 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 or different from each other, and each is independently 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. Furthermore, R7 may be hydrogen, or a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.

[0033] More specifically, R1 is an unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms or O, and R2 to R6 may be the same or different from each other, and each may independently be an unsubstituted linear alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 20 carbon atoms.

[0034] In the above cases, the phosphorus-based flame retardant compound is x - ligand and y - When forming a coordination bond between M metals together with the ligand, x is composed of substituents of chemical formula 1. - By including a ligand, the flame retardant composition containing it can maintain particularly excellent flame retardant properties while also ensuring excellent mechanical properties.

[0035] Furthermore, in the above chemical formula 1, M may be one or more selected from the group consisting of metals and ammonium ions. More specifically, M may be one or more 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. M may be one or more selected from the group consisting of Al, Zn, Mg, Ca, and ammonium ions.

[0036] Furthermore, in the aforementioned chemical formula 1, n, m, x, and y are either identical or different from each other, and each is an integer between 1 and 5, independently of the others.

[0037] Furthermore, in the aforementioned chemical formula 1, (nx + my)+ represents the cation charge of the metal element M. Specifically, nx represents the value obtained by multiplying n by x, and my represents the value obtained by multiplying m by y, and nx + my may be between 1 and 10.

[0038] On the other hand, the flame retardant compound represented by chemical formula 1 may be a coordination bond between a ligand containing one or more selected from the group consisting of a first ligand represented by the following chemical formula 2 and one or more selected from the group consisting of a second ligand represented by the following chemical formula 3, and a central metal element M. In other words, the flame retardant compound represented by chemical formula 1 may be a coordination bond between a ligand containing a total of m first ligands represented by the following chemical formula 2 and a total of n second ligands represented by the following chemical formula 3, and a central metal element M. In a preferred example, the flame retardant compound of chemical formula 1 may be a coordination bond between a ligand containing a first ligand represented by the following chemical formula 2 and a second ligand represented by the following chemical formula 3, where n and m are 1, and a central metal element M.

[0039] [Chemical formula 2] [ka]

[0040] [Chemical formula 3] [ka]

[0041] In the aforementioned chemical formulas 2 to 3, the meanings of R1 to R5, x, y, n, and m are the same as those defined above.

[0042] Specifically, the first ligand represented by chemical formula 2 is not limited to specific examples, but to give one example, the compound represented by chemical formula 1 may contain any one of the first ligands selected from the following structural formulas.

[0043] [ka]

[0044] Furthermore, while the specific examples of the second ligand represented by chemical formula 3 are not particularly limited, one example is that the compound represented by chemical formula 1 may contain any one of the second ligands selected from the following structural formulas.

[0045] [ka]

[0046] On the other hand, while the specific examples of the flame retardant compound represented by chemical formula 1 are not particularly limited, one example is that it may include any one selected from the compounds with the following structural formulas.

[0047] [ka]

[0048] While the methods for producing the flame retardant compound represented by the aforementioned chemical formula 1 are not particularly limited, one example may include a step of reacting a metal salt with a ligand precursor compound in the presence of a base.

[0049] An example of the aforementioned metal salt is Al2(SO4)3, which is an aluminum salt.

[0050] The ligand precursor compound is a compound that reacts with a base to be converted into an anionic ligand compound, and examples include phosphate compounds or carboxylate compounds.

[0051] The phosphate compound may include phosphate, phosphate, hypophosphorous acid, or derivative compounds thereof. The carboxylate compound may include carboxylate or a derivative compound thereof.

[0052] The examples of the aforementioned bases are not particularly limited and include, for example, LiOH, NaOH, TEA, Cs2CO3, or mixtures thereof.

[0053] In the presence of the aforementioned base, the examples of reaction conditions between the metal salt and the ligand precursor compound are not significantly limited, and conventionally known reaction conditions between metal salts and ligand precursor compounds can be applied without restriction.

[0054] On the other hand, according to the present invention or other embodiments, a flame-retardant resin composition comprising the flame retardant compound and binder resin of the above embodiment can be provided.

[0055] The details relating to the flame retardant compound include the details described above with respect to the embodiment described above.

[0056] The binder resin can be conventionally known thermoplastic resins, thermosetting resins, or any of these in single, blended, or copolymerized forms without limitation. Specific examples include polyester resins, polyamide resins, polyolefin resins, polyurethane resins, polyimide resins, epoxy resins, phenolic resins, and polyphenylene sulfide resins, or mixtures thereof.

[0057] Based on the total weight of solids in the flame-retardant resin composition, the content of the flame retardant compound may be 1% to 30% by weight, or 5% to 30% by weight, or 10% to 30% by weight, or 15% to 30% by weight, or 15% to 20% by weight. Furthermore, the content of the binder resin may be 70% to 99% by weight, or 70% to 95% by weight, or 70% to 90% by weight, or 70% to 85% by weight, or 80% to 85% by weight.

[0058] The total weight of solids refers to the sum of the total weights of the components of the resin composition excluding the solvent. The solids and the weight percentage based on the solids of each component can be measured using common analytical methods used in this industry, such as liquid chromatography or gas chromatography.

[0059] The aforementioned solvents include 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, and One or more substances selected from the group consisting of ruene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene 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 may be used, but are not limited thereto.

[0060] Furthermore, the flame-retardant resin composition may further contain other additives. The content of these other additives is 0.01% to 20% by weight, based on the total weight of solids in the flame-retardant resin composition.

[0061] The types, methods, and timing of addition of the aforementioned additives are not significantly limited, and a wide variety of publicly known additives can be applied without restriction. Specific examples of additives include impact reinforcers, antioxidants, compatibilizers, hydrolysis stabilizers, ultraviolet stabilizers, heat stabilizers, color additives, fixatives, flame retardant aids, fiber reinforcers, inorganic fillers, nucleating agents, lubricants, mold release agents, colorants, hydrolysis stabilizers, viscosity enhancers, fluorescent whitening agents, main chain extenders, pigments, dyes, antistatic agents, or mixtures of two or more of these.

[0062] On the other hand, the flame-retardant resin composition may have a flame retardancy rating of V0 or V1 as measured according to the UL-94 test standard. Examples of test specimens for measuring flame retardancy according to the UL-94 standard are not greatly limited. For example, the flame-retardant resin composition is mixed with a twin-screw extruder at a temperature of 230°C to 260°C, or 260°C to 280°C, the homogenized polymer strand is drawn out, cooled in a water bath, pelletized, and sufficiently dried, then processed by an injection molding machine at a melting temperature of 240°C to 270°C, or 260°C to 290°C, and a test specimen with a specification of 1.6 mm in thickness, 12.7 mm in width and 127 mm in length can be used. The flame-retardant resin composition satisfies the V0 or V1 flame retardancy rating measured according to the UL-94 test standard, and can achieve excellent flame retardant properties; when the flame retardancy measured according to the UL-94 test standard is higher than V2 rating, the flame retardant properties become poor.

[0063] On the other hand, the flame-retardant resin composition has a tensile strength measured according to ASTM D638 of 425 kgf / cm 2 or more, or 428 kgf / cm 2 or more, or 425 kgf / cm 2 to 500 kgf / cm 2 , or 428 kgf / cm 2 to 480 kgf / cm 2 . Examples of the test specimen, equipment and conditions used for measuring the tensile strength are not greatly limited, and the ASTM D638 method and conventionally known methods for measuring the tensile strength of resin molded articles can be applied without limitation. However, by way of example, specifically, after preparing 5 dumbbell-shaped test specimens respectively in accordance with ASTM D638 using UTM-5566 (Universal Testing Machine, Instron), the tensile strength of each of the 5 test 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 measured according to ASTM D638 of 425 kgf / cm 2The above conditions are met, and excellent tensile properties can be achieved, with a tensile strength of 425 kgf / cm². 2 If the value falls below a certain level, the tensile properties will be poor.

[0064] On the other hand, the flame-retardant resin composition may have an impact strength of 2.1 kgf·cm / cm or higher, 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 based on ASTM D256 (1 / 8 inch, Notched Izod). The examples of specimens, equipment, and conditions used to measure the impact strength are not significantly limited, and the ASTM D256 method and conventionally known methods for measuring the impact strength of resin molded articles can be applied without limitation. The flame-retardant resin composition can achieve excellent impact properties by satisfying the requirement of an impact strength of 2.1 kgf·cm / cm or higher, measured at 23°C based on ASTM D256 (1 / 8 inch, Notched Izod), and if the impact strength falls below 2.1 kgf·cm / cm, the impact properties become poor.

[0065] On the other hand, according to the present invention or other embodiments, a flame-retardant product containing the flame-retardant resin composition of the other embodiment can be provided.

[0066] The details relating to the flame-retardant resin composition include the details described above with respect to the other embodiments.

[0067] The flame-retardant product may include the flame-retardant resin composition of the other embodiment or a molded article thereof. The flame-retardant resin composition can be directly coated onto the product to form a flame-retardant coating layer, or it can be coated onto components constituting the product and introduced into the product.

[0068] The specific shape and size of the molded article may vary depending on its application, and the examples are not particularly limited. The examples of the molding method are not limited, and any molding method widely known in the field of resin composition molding can be applied without restriction. For example, the molded article can be obtained by molding the flame-retardant resin composition through various molding methods, such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, and profile extrusion, and post-processing methods such as thermoforming using these methods, depending on its application.

[0069] The examples of the types of products mentioned above are not very limited and may include, for example, electrical / electronic products and automotive parts. [Effects of the Invention]

[0070] According to the present invention, it is possible to provide a novel phosphorus-based flame retardant compound with a structure that can improve the flame retardant properties and mechanical properties of polymer resins, as well as flame retardant resin compositions and flame retardant products using the same. [Modes for carrying out the invention]

[0071] The present invention will be described in more detail by the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[0072] <Manufacturing Examples 1 to 6: Manufacturing of Flame Retardant Compounds> Manufacturing Example 1 The compound represented by chemical formula 1-1 was synthesized through a reaction as shown in [Reaction Equation 1] below.

[0073] [Reaction Equation 1] [ka]

[0074] The L-1 compound and diethylphosphinic acid (M-1 compound) were added to the reactor as reactants in a molar ratio of 1:2. NaOH was dissolved in water at room temperature as a base and stirred. Then, Al2(SO4)3 was added as an aluminum salt, and the temperature was raised to 100°C and the mixture was stirred for 12 hours to allow the reaction to proceed.

[0075] The solid was isolated by vacuum filtration using a suction filter, and the solid product was purified by washing with additional water and acetone (twice each). The solid product was transferred to a glass bottle, placed in a vacuum oven, and dried overnight to obtain compound 1-1. (Yield: 90%)

[0076] [Chemical formula 1-1] [ka]

[0077] Manufacturing Example 2 The compound represented by chemical formulas 1-2 was synthesized through a reaction as shown in [Reaction Equation 2] below.

[0078] [Reaction Equation 2] [ka]

[0079] The compound represented by chemical formula 1-2 was synthesized in the same manner as in Production Example 1, except that L-2 (molar ratio 1:1) was used instead of L-1 as the reactant. (Yield: 92%)

[0080] [Chemical formula 1-2] [ka]

[0081] Manufacturing Example 3 [Reaction Equation 3] The compounds represented by chemical formulas 1-3 were synthesized through a reaction like the one shown in [Reaction Equation 3] below. [ka]

[0082] The compounds represented by chemical formulas 1-3 were synthesized in the same manner as in Production Example 1, except that L-3 was used instead of L-1 and M-2 (molar ratio 1:1) was used instead of M-1 as reactants. (Yield: 88%)

[0083] [Chemical formula 1-3] [ka]

[0084] Manufacturing Example 4 [Reaction Equation 4] The compounds represented by chemical formulas 1-4 were synthesized through the reaction shown in [Reaction Equation 4] below. [ka]

[0085] The compounds represented by chemical formulas 1-4 were synthesized in the same manner as in Production Example 1, except that L-4 was used instead of L-1 and M-3 (molar ratio 1:1) was used instead of M-1 as reactants. (Yield: 91%)

[0086] [Chemical formula 1-4] [ka]

[0087] Manufacturing Example 5 [Reaction Equation 5] [ka]

[0088] The compounds represented by chemical formulas 1-5 were synthesized in the same manner as in Production Example 1, except that L-5 (molar ratio 1:2) was used instead of L-1 as the reactant. (Yield: 95%)

[0089] [Chemical formula 1-5] [ka]

[0090] Manufacturing Example 6 [Reaction Equation 6] [ka]

[0091] The compounds represented by chemical formulas 1-6 were synthesized in the same manner as in Production Example 1, except that L-6 (molar ratio 2:1) was used instead of L-1 as a reactant. (Yield: 93%)

[0092] [Chemical formula 1-6] [ka]

[0093] <Comparative Manufacturing Example 1: Manufacturing of Flame Retardant Compounds> Comparative Manufacturing Example 1 Compound A-1, described below, was used as comparative manufacturing example 1.

[0094] [Compound A-1] [ka]

[0095] <Examples 1 to 6: Production of flame-retardant resin compositions> A flame-retardant resin composition was produced using the compounds of chemical formulas 1-1 to 1-6 mentioned above as phosphorus-based flame retardants.

[0096] According to the composition shown in Table 1 below, 85% by weight of thermoplastic resin and 15% by weight of phosphorus-based flame retardant were mixed in a mixer for 5 to 20 minutes, based on the total weight of solids in the flame retardant resin composition. The mixture was 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 test specimens for physical property measurement.

[0097] [Table 1]

[0098] <Comparative Example 1: Production of Flame-Retardant Resin Composition> Comparative Example 1 As shown in Table 1 above, the resin composition was produced in the same manner as in Example 1, except that compound A-1 obtained in Comparative Production Example 1 was used instead of phosphorus-based flame retardant compound 1-1 obtained in Production Example 1.

[0099] <Experimental Example: Measurement of Physical Properties of Flame-Retardant Resin Compositions> The physical properties of the flame-retardant resin compositions obtained in the above examples and comparative examples were measured by the following method, and the results are shown in Table 3.

[0100] 1. Flame retardant properties The flame-retardant components obtained in the above practical examples and comparative examples were mixed with polymer pellets and optional additives, and the mixture was prepared 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 out, cooled in a water bath, and then pelletized.

[0101] After thorough drying, the molded composition was processed in an injection molding machine at a melting temperature of 240°C to 270°C or 260°C to 290°C to obtain test specimens. Using test specimens 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.

[0102] Specifically, a 20mm high flame was applied to the specimen for 10 seconds, and the burning time t1 of the specimen was measured to record the combustion pattern. Next, after the initial flame application and once combustion had finished, the flame was applied again for 10 seconds, and the burning time t2 and spark formation time (glowing time) t3 of the specimen were measured to record the combustion pattern. After applying the same procedure to five specimens, they were evaluated according to the criteria in Table 2 below.

[0103] [Table 2]

[0104] 2. Properties other than flame retardancy (1) Tensile strength: Measured according to the ASTM D638 method. Specifically, using a UTM-5566 (Universal Testing Machine, Instron), five dumbbell-shaped specimens were prepared according to the ASTM D638 specifications, and the tensile strength of each of the five specimens was measured at a speed of 50 mm / min. The average value was used to show the results. (2) Izod impact strength at room temperature: Measured at 23°C based on ASTM D256 (1 / 8 inch, Notched Izod).

[0105] Results of the experimental example [Table 3]

[0106] As shown in Table 3 above, the flame-retardant resin compositions obtained in Examples 1 to 6 were more effective than those in Comparative Example 1, with x being composed of substituents of chemical formula 1. - By including a phosphorus-based flame retardant compound, which is a metal coordination compound containing a ligand, it was confirmed that the compound has an UL rating of VO or V1, excellent flame retardancy, and simultaneously high tensile strength and impact strength.

[0107] In contrast, Comparative Example 1 is composed of x of the substituent of chemical formula 1. -Even when a common phosphorus-based flame retardant compound without ligands was included and exhibited an UL rating for VO, 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] 【Chemistry 21】 In the aforementioned chemical formula 1, R １ This includes substituted or unsubstituted linear or branched alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted heteroarylene groups, O, S, or NR ７ And, R ２ , R ５ and R ６ These are, either identical or different from each other, and 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. R ３ and R ４ These are identical or different from each other, and each is independently a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkylaryl group. R ７ is hydrogen, or a substituted or unsubstituted alkyl group. M is one or more selected from the group consisting of metals and ammonium ions. n, m, x, and y are integers between 1 and 5, and are either identical or distinct from one another, and are independent of each other.

2. In the aforementioned chemical formula 1, The aforementioned R １ represents a substituted or unsubstituted linear or branched alkylene group, O or NR ７ , wherein The aforementioned R ２ , R ５ and R ６ These are identical or different from each other, and each is independently a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group. The aforementioned R ３ and R ４ These are identical or different from each other, and each is independently a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group. R ７ The flame retardant compound according to claim 1, wherein is hydrogen, or a substituted or unsubstituted alkyl group.

3. In the aforementioned chemical formula 1, The aforementioned R １ This is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, O, or NR ７ And, The aforementioned R ２ , R ５ and R ６ These are identical or different from each other, and each is independently 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. The aforementioned R ３ and R ４ The flame retardant compound according to claim 1, wherein each of the members is identical or different from the others and is independently 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. The flame retardant compound according to claim 1, wherein M is one or more 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. The flame retardant compound according to claim 4, wherein M is one or more selected from the group consisting of Al, Zn, Mg, Ca, and ammonium ions.

6. The flame retardant compound according to claim 1, wherein the flame retardant compound represented by chemical formula 1 is a coordination bond between a ligand selected from the group consisting of a first ligand represented by the following chemical formula 2 and a second ligand selected from the group consisting of a second ligand represented by the following chemical formula 3, and a central metal element M. [Chemical formula 2] 【Chemistry 22】 [Chemical formula 3] 【Chemistry 23】 In the aforementioned chemical formulas 2 to 3, R １ R ６ The details regarding x, y, n, and m are the same as the definitions in Claim 1.

7. The flame retardant compound according to claim 1, wherein the flame retardant compound represented by chemical formula 1 includes one selected from the compounds with the following structural formulas. 【Chemistry 24】

8. A flame-retardant resin composition comprising the flame retardant compound described in claim 1; and a binder resin.

9. The flame-retardant resin composition according to claim 8, wherein the binder resin comprises polyester or polyamide.

10. The flame-retardant resin composition according to claim 8, wherein the content of the flame retardant compound is 1% by weight to 30% by weight, based on the total weight of solids in the flame-retardant resin composition.

11. A flame-retardant product comprising the flame-retardant resin composition described in claim 8.

Images