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] Mutual citation with related applications This application claims priority rights based on Korean Patent Application No. 10-2024-0033940 dated March 11, 2024, and Korean Patent Application No. 10-2025-0023564 dated February 24, 2025, and all content disclosed in the documents of said Korean Patent Applications is included 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 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,

[0014] 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 NR5.

[0015] R2 to R4, which are the same as or different from each other, are each independently hydrogen, a hydroxy group, a substituted or unsubstituted linear or branched alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

[0016] R5 is hydrogen, a hydroxy group, a substituted or unsubstituted linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group,

[0017] M is one or more selected from the group consisting of metals and ammonium ions,

[0018] x and y, which are the same as or different from each other, are each independently an integer of 1 to 5,

[0019] n is an integer of 1 to 5,

[0020] m is an integer of 0 to 5.

[0021] This specification further provides a flame-retardant resin composition comprising the flame retardant compound; and a binder resin;

[0022] This specification further provides a flame-retardant product comprising the flame-retardant resin composition.

[0023] Hereinafter, the flame retardant compound according to specific embodiments of the present invention, and the flame-retardant resin composition and flame-retardant product using the same will be described in more detail.

[0024] In this specification, when a certain part "comprises" a component, this does not exclude other components unless specifically stated to the contrary, and it means that other components may be further included.

[0025] In this specification, examples of substituents are described below, but the present invention is not limited thereto.

[0026] In this specification, the term “substitution” means that another functional group is bonded in place of a hydrogen atom in a compound, and the substitution site is not limited to a position where a hydrogen atom is substituted, i.e., any position where a substituent can be substituted, and if two or more substituents are substituted, the two or more substituents may be the same or different from one another.

[0027] In this specification, the term “substituted or unsubstituted” means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen groups; cyano groups; nitro groups; hydroxyl groups; carbonyl groups; ester groups; imide groups; amide groups; amino groups; carboxyl groups; sulfonic acid groups; sulfonamide groups; phosphine oxide groups; alkoxy groups; aryloxy groups; alkylthiooxy groups; arylthiooxy groups; alkylsulfoxy groups; arylsulfoxy groups; silyl groups; boron groups; alkyl groups; cycloalkyl groups; alkenyl groups; aryl groups; aralkyl groups; aralkenyl groups; alkylaryl groups; arylphosphine groups; or heterocyclic groups containing one or more N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked together from the substituents exemplified above. For example, “substituents with two or more substituents linked together” may be biphenyl groups. That is, a biphenyl group may be an aryl group and may be interpreted as a substituent with two phenyl groups linked together.

[0028] 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.

[0029] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic or 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.

[0030] In this specification, a heteroaryl group contains one or more non-carbon atoms, or heteroatoms, and specifically, the heteroatoms may contain 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, 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, and benzo Examples of heteroaryl groups include, but are not limited to, thiazolyl, benzocarbazolyl, benzothiophene, dibenzothiophene, 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 groups may be substituted or unsubstituted, and examples of substituents are as described above.

[0031] According to one embodiment of the present invention, a flame retardant compound represented by the following chemical formula 1 can be provided.

[0032] [Chemical formula 1] [ka]

[0033] In the aforementioned chemical formula 1,

[0034] 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 NR5.

[0035] R2 through R4 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 cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0036] R5 is hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group.

[0037] M is one or more selected from the group consisting of metals and ammonium ions.

[0038] x and y are either identical or different from each other, and are independently integers between 1 and 5.

[0039] n is an integer between 1 and 5.

[0040] m is an integer between 0 and 5.

[0041] The inventors of the present invention have completed their invention by confirming 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. Furthermore, the flame retardant compound represented by the above-mentioned chemical formula 1 not only increases the flame retardant properties of thermoplastic resin compositions when applied in the same amount compared to conventional halogen-based flame retardants, but also exhibits sufficient flame retardancy even when using a smaller amount compared to existing flame retardants, thereby providing flame retardant products with superior flame retardancy more effectively.

[0042] 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.

[0043] 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 R1 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.

[0044] In the above chemical formula 1, R1 is defined as NR5, where R5 may be hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group.

[0045] In the above chemical formula 1, the alkyl, aryl, and heteroaryl groups defined as R2 to R4 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 R4 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 R4 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.

[0046] In one preferred embodiment, in the above chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene group, O, or NR5; R2 to R4 are identical or different from each other and are independently a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group, and R5 may be hydrogen, or a substituted or unsubstituted linear or branched alkyl group.

[0047] Specifically, according to other embodiments 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 NR5, in which case R2 to R4 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, and R5 may be hydrogen. More specifically, R1 is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, O, or NR5, R2 is an unsubstituted linear alkyl group having 1 to 20 carbon atoms or an unsubstituted aryl group having 6 to 20 carbon atoms, R3 and R4 may be the same or different from each other, and each may independently be a linear alkyl group having 1 to 20 carbon atoms, and R5 may be hydrogen.

[0048] 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.

[0049] Furthermore, in the aforementioned chemical formula 1, x and y may be the same or different from each other, and may independently be integers from 1 to 5 or integers from 1 to 3.

[0050] n is an integer between 1 and 5 or an integer between 1 and 3, and m may be an integer between 0 and 5 or an integer between 1 and 5 or an integer between 1 and 3.

[0051] 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 and x, and my represents the value obtained by multiplying m and y, and nx + my may be between 1 and 10.

[0052] In the above case, the flame retardant compound, through the configuration of a first phosphorus ligand having R1 and R2 substituents and a second phosphorus ligand having R3 and R4 substituents contained in its structure, further enhances the coordination bond effect between metals, maintaining excellent flame retardant properties and ensuring mechanical properties equivalent to or better than existing ones. In other words, in the present invention, x composed of substituents of the above chemical formula 1 is - By including a phosphorus-based flame retardant compound, which is a metal coordination compound containing a ligand, it is possible to improve the excellent flame retardancy, tensile strength, and impact strength of VO to a level exceeding UL grade.

[0053] On the other hand, the flame retardant compound represented by chemical formula 1 may be a coordination bond between a central metal element M and one or more ligands selected from the group consisting of a first ligand represented by the following chemical formula 2 and one or more ligands selected from the group consisting of a second ligand represented by the following chemical formula 3. In other words, the flame retardant compound represented by chemical formula 1 may be a coordination bond between a total of n first ligands represented by the following chemical formula 2, a total of m second ligands represented by the following chemical formula 3, or a mixture of two or more of these 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.

[0054] [Chemical formula 2] [ka]

[0055] [Chemical formula 3] [ka]

[0056] 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.

[0057] 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.

[0058] [ka]

[0059] 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.

[0060] [ka]

[0061] 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.

[0062] [ka]

[0063] 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.

[0064] An example of the aforementioned metal salt is Al2(SO4)3, which is an aluminum salt.

[0065] 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. The phosphate compound may include phosphate, phosphate, hypophosphorous acid, or derivative compounds thereof. The carboxylate compound may include carboxylate or a derivative compound thereof.

[0066] The examples of the aforementioned bases are not particularly limited and include, for example, LiOH, NaOH, TEA, Cs2CO3, or mixtures thereof.

[0067] 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.

[0068] On the other hand, according to yet another embodiment of the invention, a flame-retardant resin composition comprising the flame retardant compound and binder resin of the above embodiment can be provided.

[0069] The details relating to the flame retardant compound include the details described above with respect to the embodiment described above.

[0070] 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.

[0071] Furthermore, by using the flame retardant compound of chemical formula 1, the flame retardant resin composition can improve flame retardancy while maintaining superior mechanical properties compared to existing halogen-based or general flame retardants of the same content. In addition, even if the flame retardant compound of chemical formula 1 is used in the thermoplastic flame retardant resin composition in a relatively smaller amount than conventionally used, sufficient flame retardancy can be achieved, providing a flame retardant product with excellent flame retardancy.

[0072] In one embodiment, the content of the flame retardant compound in the flame retardant resin composition may be 1% to 30% by weight, 5% to 30% by weight, 10% to 30% by weight, 15% to 30% by weight, 15% to 20% by weight, or 1% to 5% by weight, based on the total weight of the solids in the flame retardant resin composition. The content of the binder resin is included as a remainder, and specifically may be 70% to 99% by weight, 70% to 95% by weight, 70% to 90% by weight, 70% to 85% by weight, 80% to 85% by weight, or 95% to 99% by weight.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] On the other hand, the flame retardant resin composition may have a flame retardancy of VO or V1 grade as measured by the UL-94 test standard. The examples of test pieces 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 in a twin-screw extruder at a temperature of 230°C to 260°C or 260°C to 280°C, the homogenized polymer strands may be drawn, cooled in a water bath, pelletized, thoroughly dried, and then processed in an injection molding machine at a melting temperature of 240°C to 270°C or 260°C to 290°C to produce test pieces with a thickness of 1.6 mm, a width of 12.7 mm, and a length of 127 mm. The flame retardant resin composition can achieve excellent flame retardancy by satisfying a flame retardancy of VO or V1 grade as measured by the UL-94 test standard, and if the flame retardancy measured according to the UL-94 test standard is higher than V2 grade, the flame retardancy will be poor.

[0078] On the other hand, the flame-retardant resin composition has a tensile strength of 425 kgf / cm² as measured according to the ASTM D638 method. 2 Above or above, or 428 kgf / cm² 2 Above 425 kgf / cm² 2 or 500 kgf / cm² 2 , or 428 kgf / cm² 2 or 480 kgf / cm² 2 It may also be the case that the specimens, equipment, and conditions used for measuring the tensile strength are not significantly limited, and the ASTM D638 method and conventionally known methods for measuring the tensile strength of resin molded articles can be applied without restriction. However, to give one example, specifically, five dumbbell-shaped specimens can be prepared according to the ASTM D638 standard using a UTM-5566 (Universal Testing Machine, Instron), and the tensile strength of each of the five specimens can be measured at a speed of 50 mm / min, and the result can be shown as the average value. The flame-retardant resin composition has a tensile strength of 425 kgf / cm² as measured according to the ASTM D638 method. 2Satisfying the above requirements enables excellent tensile properties to be achieved, and when the tensile strength is lower than 425 kgf / cm 2 , the tensile properties become poor.

[0079] On the other hand, the flame-retardant resin composition may have an impact strength measured at 23°C in accordance with ASTM D256 (1 / 8 inch, Notched Izod) 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. Examples of test specimens, equipment and conditions used for measuring the impact strength are not greatly 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 satisfies the requirement that the impact strength measured at 23°C in accordance with ASTM D256 (1 / 8 inch, Notched Izod) is 2.1 kgf·cm / cm or more, thereby enabling excellent impact properties to be achieved, and when the impact strength is lower than 2.1 kgf·cm / cm, the impact properties become poor.

[0080] On the other hand, according to another embodiment of the invention, a flame-retardant product including the flame-retardant resin composition of said another embodiment can be provided.

[0081] The content related to said flame-retardant resin composition includes the content described above with respect to said another embodiment.

[0082] Said flame-retardant product may include the flame-retardant resin composition of said another embodiment, or a molded article thereof. The flame-retardant resin composition can be directly coated on a product to form a flame-retardant coating layer, or can be coated on a component constituting the product and introduced into the product.

[0083] The specific shape and size of the molded article can vary depending on its application, and examples are not particularly limited. The molding method is also 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 using a variety of molding methods, such as injection molding, extrusion, extrusion blow molding, injection blow molding, and profile extrusion, as well as post-processing methods such as thermoforming using these methods, depending on its application.

[0084] 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]

[0085] 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]

[0086] 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.

[0087] <Manufacturing Examples 1 to 3: 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.

[0088] [Reaction Equation 1] [ka]

[0089] The L-1 compound and diethylphosphinic acid (M-1 compound) were added to the reactor as reactants in a molar ratio of 1:3. As a base, LiOH was dissolved in water at room temperature and stirred. Then, Al2(SO4)3 was added as an aluminum salt, and the temperature was raised to 100°C and stirred for 12 hours to allow the reaction to proceed.

[0090] After the reaction was complete, 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: 89%)

[0091] [Chemical formula 1-1] [ka]

[0092] Manufacturing Example 2 [ka]

[0093] 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 1:3) was used instead of L-1 as the reactant. (Yield: 92%)

[0094] [Chemical formula 1-2] [ka]

[0095] Manufacturing Example 3 [ka]

[0096] The compounds represented by chemical formulas 1-3 were synthesized in the same manner as in Production Example 1, except that L-3 (molar ratio 1:3) was used instead of L-1 as a reactant. (Yield: 92%)

[0097] [Chemical formula 1-3] [ka]

[0098] Manufacturing Example 4 [ka]

[0099] The compounds represented by chemical formulas 1-4 were synthesized in the same manner as in Production Example 1, except that L-1 was used alone as a reactant. (Yield: 85%)

[0100] [Chemical formula 1-4] [ka]

[0101] Manufacturing Example 5 [ka]

[0102] The compounds represented by chemical formulas 1-5 were synthesized in the same manner as in Production Example 1, except that L-4 (molar ratio 1:3) was used instead of L-1 as a reactant. (Yield: 93%)

[0103] [Chemical formula 1-5] [ka]

[0104] Manufacturing Example 6 [ka]

[0105] The compounds represented by chemical formulas 1-6 were synthesized in the same manner as in Production Example 1, except that L-5 (molar ratio 1:3) was used instead of L-1 as a reactant. (Yield: 92%)

[0106] [Chemical formula 1-6] [ka]

[0107] <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.

[0108] [Compound A-1] [ka]

[0109] Comparative Manufacturing Example 2 Compound A-2, described below, was used as comparative manufacturing example 2.

[0110] [Compound A-2] [ka]

[0111] <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.

[0112] 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 specimens for physical property measurement.

[0113] [Table 1]

[0114] <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.

[0115] Comparative Example 2 A resin composition was produced in the same manner as in Example 1, except that compound A-2 (phosphorus-based flame retardant 8) was used instead of the phosphorus-based flame retardant compound 1-1 obtained in Production Example 1.

[0116] [Compound A-2] [ka] (Example: In the above chemical formula, R 1 , R 2 =methyl, R 3 = methylene, M=Al, n, m, x=1)

[0117] <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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] [Table 2]

[0122] 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.

[0123] (2) Izod impact strength at room temperature: Measured at 23°C based on ASTM D256 (1 / 8 inch, Notched Izod).

[0124] Results of the experimental example [Table 3]

[0125] As shown in Table 3 above, the flame-retardant resin compositions obtained in Examples 1 to 6 are more effective than those in Comparative Examples 1 and 2, as they are 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 VO has an UL rating, exhibits superior flame retardancy at a level equivalent to or higher than existing products, and simultaneously demonstrates high tensile strength and impact strength.

[0126] In contrast, Comparative Examples 1 and 2 have x of chemical formula 1. - It contains a common phosphorus-based flame retardant compound that does not contain ligands and exhibits UL-grade flame retardant properties for VO, but its tensile strength and impact strength are lower than those of the examples.

Claims

1. A flame retardant compound represented by the following chemical formula 1. [Chemical formula 1] 【Chemistry 23】 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 ５ And, R ２ R ４ These 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 cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ５ is hydrogen, a hydroxyl group, a substituted or unsubstituted linear or branched alkyl group, a cycloalkyl group, or a substituted or unsubstituted aryl group. M is one or more selected from the group consisting of metals and ammonium ions. x and y are either identical or different, and each is an integer between 1 and 5, independently of the other. n is an integer between 1 and 5. m is an integer between 0 and 5.

2. In the aforementioned chemical formula 1, The aforementioned R １ is a substituted or unsubstituted linear or branched alkylene group, O or NR ５ And, The above R ２ to R ４ are the same 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 ５ The flame retardant compound according to claim 1, wherein is hydrogen, or a substituted or unsubstituted linear or branched 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 ５ Therefore, in such a case, R ２ R ４ These are identical 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, R ５ The flame retardant compound according to claim 2, wherein is hydrogen.

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 represented by the chemical formula 1 is, The flame retardant compound according to claim 1, which is a coordination bond between one or more ligands selected from the group consisting of a first ligand represented by the following chemical formula 2 and one or more ligands 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 24】 [Chemical formula 3] 【Chemistry 25】 In the aforementioned chemical formulas 2 to 3, R １ R ４ The details regarding x, y, n, and m are the same as those defined 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 26】

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.

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