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

Abstract

The present disclosure relates to a flame retardant compound of a novel structure having excellent flame retardant properties and improved mechanical properties, and to a flame retardant resin composition and a flame retardant product using the same.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2024-0011859, filed with the Korean Intellectual Property Office on January 25, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0003] This disclosure relates to flame-retardant compounds, flame-retardant resin compositions using the same, and flame-retardant products. More specifically, it relates to flame-retardant compounds capable of improving the flame-retardant and mechanical properties of polymer resins, and to flame-retardant resin compositions and flame-retardant products using the same. Background Technology

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

[0005] Methods exist for imparting flame retardancy, such as polymerization involving flame-retardant monomers, and mixing flame retardants or flame-retardant additives with the produced resin. Flame retardants include halogenated flame retardants, as well as non-halogenated flame retardants such as phosphorus-based, nitrogen-based, and hydroxide-based flame retardants. Flame-retardant additives include antimony compounds, silicon-based compounds, and zinc-based compounds, etc.

[0006] Halogenated flame retardants are the most common because they offer higher flame retardant efficiency compared to non-halogenated flame retardants and can maintain the mechanical properties of the resin, with brominated flame retardants being particularly effective. However, if brominated flame retardants are added during resin processing, the high temperature and pressure generated during processing reduce thermal stability, leading to decomposition and, as a result, the production of corrosive and toxic gases, which negatively impact both the working environment and human health.

[0007] To avoid these problems, the use of non-halogenated flame retardants is available, with the use of non-halogenated flame retardant compounds being widely adopted. However, non-halogenated flame retardant compounds have the following disadvantages due to their lower flame retardant efficiency compared to halogenated flame retardants: excessive amounts of non-halogenated flame retardant compounds must be added, and sufficient flame retardancy is difficult to achieve in thermoplastic resin compositions where a char layer cannot be formed due to the principles of phosphorus-based flame retardant systems.

[0008] Therefore, there is a need to develop non-halogenated flame retardants suitable for improving the flame retardancy of polymer resins. Summary of the Invention

[0009] Technical issues

[0010] One object of the present invention is to provide flame retardant compounds that can improve the flame retardant properties and mechanical properties of polymer resins.

[0011] Another object of this disclosure is to provide a flame-retardant resin composition comprising the flame-retardant compound.

[0012] Another object of this disclosure is to provide flame-retardant products comprising the flame-retardant resin composition.

[0013] Technical solution

[0014] This specification provides flame retardant compounds represented by the following chemical formula 1:

[0015] [Chemical Formula 1]

[0016]

[0017] In chemical formula 1,

[0018] R1 is a substituted or unsubstituted linear or branched alkylene, a substituted or unsubstituted arylene, a substituted or unsubstituted heteroarylene, O, S, or NR7.

[0019] R2, R5, and R6 may be the same as or different from each other, and each may independently be hydrogen, hydroxyl, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0020] R3 and R4 may be the same as or different from each other, and each may independently be a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl.

[0021] R7 is hydrogen or a substituted or unsubstituted alkyl group.

[0022] M is selected from one or more metal ions and ammonium ions.

[0023] n, m, x, and y may be the same or different from each other, and each is an independent integer from 1 to 5.

[0024] Furthermore, this specification provides a flame-retardant resin composition comprising the flame-retardant compound and the binder resin.

[0025] In addition, flame-retardant products comprising the flame-retardant resin composition are provided in this specification.

[0026] The flame retardant compounds according to specific embodiments of the present invention, as well as flame retardant resin compositions and flame retardant products using the same, will be described in more detail below.

[0027] In this specification, unless otherwise specifically stated, when a part is described as "containing" a component, it means that it may also contain other components.

[0028] Examples of substituents are described below in this specification, but are not limited thereto.

[0029] In this specification, the term "substitution" means that a functional group other than a hydrogen atom is bonded to the compound, and there is no restriction on the position of substitution, as long as it is a position where a hydrogen atom can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0030] In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from: deuterium; halogen group; cyano; nitro; hydroxyl; carbonyl; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; aryl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aryl-alkenyl group; alkyl aryl group; arylphosphyl group; or heterocyclic group containing one or more of N, O, and S atoms, or substituted with substituents connected to two or more of the exemplified substituents. For example, "substituents connected to two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or can be interpreted as substituents connected to two phenyl groups.

[0031] In this specification, the alkyl group can 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. In addition, 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, 5-methylhexyl, etc. Alkyl groups can be substituted or unsubstituted, and in the case of substitution, examples of substituents are as described above.

[0032] In this specification, the aryl group is not particularly limited, but it is preferably a group having 6 to 60 carbon atoms, and can be a monocyclic aryl or polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Monocyclic aryl groups may include, but are not limited to, phenyl, biphenyl, terphenyl, etc. Polycyclic aryl groups may include naphthyl, anthraceneyl, phenanthryl, pyrene, etc. base, Aryl, fluorene, etc., but not limited to these. Aryl groups can be substituted or unsubstituted, and in the case of substitution, examples of substituents are as described above.

[0033] In this specification, a heteroaryl group comprises one or more heteroatoms that are non-carbon atoms, specifically one or more atoms selected from O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 60, and the heteroaryl group can be monocyclic or polycyclic. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazolyl, and thiazolyl. azole group, Diazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridineyl, pyridazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazenopyrazinyl, isoquinolinyl, indoleyl, carbazoleyl, benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthrolinel, thiazolyl, iso azole group, The aryl groups are diazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, aziridinyl, azindolyl, isoindolyl, indazole, purine, pteridinyl, β-carbolinyl, naphridinyl, tert-pyridinyl, pheridinyl, imidazopyridinyl, pyrrolopyridinyl, azoxyl, pyrazolyl, and dibenzofuranyl, but are not limited to these. The heteroaryl group can be substituted or unsubstituted, and in the case of substitution, examples of substituents are as described above.

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

[0035] [Chemical Formula 1]

[0036]

[0037] In chemical formula 1,

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

[0039] R2, R5, and R6 may be the same as or different from each other, and each may independently be hydrogen, hydroxyl, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0040] R3 and R4 may be the same as or different from each other, and each may independently be a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl.

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

[0042] M is selected from one or more metal ions and ammonium ions.

[0043] n, m, x, and y may be the same or different from each other, and each is an independent integer from 1 to 5.

[0044] The inventors have experimentally determined and completed the present invention, as represented by Chemical Formula 1, which, when used as a flame retardant, significantly improves the flame retardant and mechanical properties of the polymer resin (i.e., binder resin) contained in a flame-retardant resin composition by applying a compound obtained through coordination bonding between two types of phosphorus-based ligands with specific structures and a metal element. Furthermore, compared to conventional halogen-based flame retardants, when applied in the same amount, the flame-retardant compound represented by Chemical Formula 1 not only improves the flame retardant properties of thermoplastic resin compositions but also exhibits sufficient flame retardancy even when used in smaller amounts than existing flame retardants, thus providing a more effective and superior flame-retardant product.

[0045] Specifically, flame-retardant compounds used to improve the flame-retardant properties of polymer resins may contain two types of repeating ligand units represented by the above chemical formula 1.

[0046] In Formula 1, the alkylene, arylene, and heteroaryl groups defined in R1 can 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 heteroaryl groups of R1 can each be independently substituted by one or more substituents selected from: deuterium; halogen group; cyano; nitro; hydroxyl; carbonyl; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; aryl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aryl-alkenyl group; alkyl aryl group; arylphosphyl group; and heteroaryl group. Specifically, the alkylene, arylene, and heteroaryl groups of R2 to R5 may each be independently substituted by one or more of the following substituents: deuterium; halogen group; cyano; nitro; hydroxyl; amide group; carboxyl group; alkyl group; aryl group; and heteroaryl group.

[0047] In Formula 1, the alkyl, aryl, and heteroaryl groups defined in R2 to R6 can 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 in R2 to R6 are each independently substituted with one or more substituents selected from: deuterium; halogen; cyano; nitro; hydroxyl; carbonyl; ester; imide; amide; amino; carboxyl; sulfonyl; sulfonamide; phosphine oxide; alkoxy; aryloxy; alkylthio; arylthio; alkylsulfonyl; arylsulfonyl; silyl; boron; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylene; alkylaryl; arylphosphine; and heteroaryl. Specifically, the alkyl, aryl, and heteroaryl groups of R2 to R6 may each be independently substituted by one or more substituents selected from the following: deuterium; halogen; cyano; nitro; hydroxyl; amide; carboxyl; alkyl; aryl; and heteroaryl.

[0048] Furthermore, according to a preferred embodiment, in the above chemical formula 1, R1 is a substituted or unsubstituted linear or branched alkylene, O, or NR7; R2, R5, and R6 are the same or different from each other and are each independently a substituted or unsubstituted linear or branched alkyl or a substituted or unsubstituted aryl; R3 and R4 are the same or different from each other and are each independently a substituted or unsubstituted linear or branched alkyl or a substituted or unsubstituted aryl; and R7 can be hydrogen or a substituted or unsubstituted alkyl.

[0049] Specifically, according to one embodiment of the invention, in 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 may be the same as 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 may be the same as 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.

[0050] 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 as or different from each other, and may each be an unsubstituted linear alkyl group having 1 to 20 carbon atoms, or an unsubstituted aryl group having 6 to 20 carbon atoms.

[0051] In the aforementioned case, when a phosphorus-based flame retardant compound is produced by comprising x consisting of substituents of Formula 1... - The ligands thus form in the M metal and x - ligands and y - When ligands form coordination bonds, flame-retardant compositions containing them can particularly maintain excellent flame-retardant properties and also ensure excellent mechanical properties.

[0052] Furthermore, in Formula 1, M can be one or more selected from metal ions and ammonium ions. More specifically, M can be one or more selected from Mg ions, Ca ions, Al ions, Sb ions, Sn ions, Ge ions, Ti ions, Zn ions, Fe ions, Zr ions, Ce ions, Bi ions, Sr ions, Mn ions, Li ions, Na ions, K ions, and ammonium ions. M can be one or more selected from Al ions, Zn ions, Mg ions, Ca ions, and ammonium ions.

[0053] Furthermore, in chemical formula 1, n, m, x, and y are either the same as or different from each other, and each is an independent integer from 1 to 5.

[0054] Furthermore, in chemical formula 1, (nx+my) + This refers to the total cation charge of the metallic element M. Specifically, nx refers to the value obtained by multiplying n and x, and my refers to the value obtained by multiplying m and y, and nx + my can be from 1 to 10.

[0055] Simultaneously, the flame-retardant compound represented by Chemical Formula 1 can be a coordination compound between a ligand and a central metal element M, wherein the ligand comprises one or more first ligands selected from those represented by Chemical Formula 2 and one or more second ligands selected from those represented by Chemical Formula 3. That is, the coordination compound between the ligand and the central metal element M can be a flame-retardant compound represented by Chemical Formula 1, wherein the ligand comprises a total of n first ligands represented by Chemical Formula 2 and a total of m second ligands represented by Chemical Formula 3. According to a preferred embodiment, the flame-retardant compound of Chemical Formula 1 can be a coordination compound between a ligand and a central metal element M, wherein the ligand comprises a first ligand represented by Chemical Formula 2 and a second ligand represented by Chemical Formula 3, where n and m are 1.

[0056] [Chemical Formula 2]

[0057]

[0058] [Chemical Formula 3]

[0059]

[0060] In the above chemical formulas 2 to 3, the restrictions on R1 to R5, x, y, n and m are the same as those described above.

[0061] Specifically, the first ligand represented by the above chemical formula 2 is not particularly limited to specific examples, but for example, the compound represented by the above chemical formula 1 may contain any of the first ligands selected from the following structural formulas.

[0062]

[0063] Furthermore, the second ligand represented by the above chemical formula 3 is not particularly limited to specific examples, but for example, the compound represented by the above chemical formula 1 may contain any of the second ligands selected from the following structural formulas.

[0064]

[0065] Meanwhile, the flame retardant compound represented by chemical formula 1 is not particularly limited to specific examples, but may include, for example, any of the compounds selected from the following structural formulas.

[0066]

[0067] There are no particular limitations on examples of methods for preparing flame-retardant compounds represented by Formula 1, but for example, it may include a process of reacting a metal salt with a ligand precursor compound in the presence of a base.

[0068] An example of a metal salt is an aluminum salt, such as Al2(SO4)3.

[0069] A ligand precursor compound is a compound that reacts with a base to form a ligand compound in an anionic form; it can be a phosphate compound or a carboxylic acid compound. Phosphate compounds can include phosphoric acid, phosphorous acid, hypophosphite, or derivatives of each of these. Carboxylic acid compounds can include carboxylic acids or their derivatives.

[0070] There are no particular limitations on the examples of alkalis, and they may include, for example, LiOH, NaOH, TEA, Cs2CO3, or mixtures thereof.

[0071] There are no particular limitations on the examples of reaction conditions between metal salts and ligand precursor compounds in the presence of a base, and conventionally known reaction conditions between metal salts and ligand precursor compounds can be applied without restriction.

[0072] Meanwhile, according to another embodiment of the present invention, a flame-retardant resin composition can be provided, the flame-retardant resin composition comprising a flame-retardant compound of one embodiment; and an adhesive resin.

[0073] The content related to flame retardant compounds includes the above details regarding one implementation scheme.

[0074] Adhesive resins can be used in a variety of forms, not limited to conventionally known thermoplastic resins, thermosetting resins, or their individual, blended, or copolymerized forms. Specific examples include polyester resins, polyamide resins, polyolefin resins, polyurethane resins, polyimide resins, epoxy resins, phenolic resins, and polyphenylene sulfide resins, or mixtures thereof.

[0075] Based on the total weight of solids in the flame-retardant resin composition, the content of the flame-retardant compound can be from 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 can be from 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.

[0076] The total weight of solid contents refers to the sum of the weights of the components in the resin composition excluding the solvent. The weight percentage standard is based on solid content, and the solid content of each component can be measured using conventional analytical methods used in the relevant industry, such as liquid chromatography or gas chromatography.

[0077] Solvents may include one or more of the following: acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-di ...ethyl isobutyl ketone, tetrahydrofuran, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl iso Alkane, 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, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethylene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, tert-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, but not limited to these.

[0078] In addition, the flame-retardant resin composition may also contain other additives. The content of these other additives ranges from 0.01% to 20% by weight, based on the total weight of solids in the flame-retardant resin composition.

[0079] There are no particular restrictions on the type, method of addition, or timing of addition of other additives, and a wide variety of known additives may be used without limitation. Specific examples of additives include impact modifiers, antioxidants, compatibilizers, hydrolytic stabilizers, UV stabilizers, heat stabilizers, color additives, fixatives, flame retardants, fiber reinforcing agents, inorganic fillers, nucleating agents, lubricants, mold release agents, colorants, hydrolytic stabilizers, viscosity enhancers, fluorescent whitening agents, chain extenders, pigments, dyes, antistatic agents, or mixtures of two or more of these.

[0080] Simultaneously, the flame-retardant resin composition can possess a flame retardancy rating of VO or V1 as measured according to the UL-94 test standard. There are no particular limitations on the examples of specimens for which flame retardancy is measured according to the UL-94 standard; however, for example, it can be a specimen with dimensions of 1.6 mm thickness, 12.7 mm width, and 127 mm length, wherein the flame-retardant resin composition can be mixed in a twin-screw extruder at a temperature of 230°C to 260°C or 260°C to 280°C to stretch a homogenized polymer filament, which is then cooled in a water bath, granulated, and thoroughly dried, subsequently processed in an injection molding machine at a melt temperature of 240°C to 270°C or 260°C to 290°C. Excellent flame-retardant properties can be achieved by meeting a VO or V1 rating as measured according to the UL-94 test standard. However, if the flame retardancy rating measured according to the UL-94 test standard increases to V2 or higher, the flame retardant properties deteriorate.

[0081] Meanwhile, the flame-retardant resin composition can have a value of 425 kgf / cm² as measured according to ASTM D638. 2 Or larger, or 428 kgf / cm2 Or larger, or 425 kgf / cm 2 Up to 500 kgf / cm 2 Or 428 kgf / cm 2 Up to 480 kgf / cm 2 The tensile strength of the sample is determined. There are no particular restrictions on the specimens, equipment, and conditions used to measure the tensile strength, and the ASTM D638 method and conventionally known methods for measuring the tensile strength of resin molded products can be applied without limitation. However, specifically, for example, using a UTM-5566 (Universal Testing Machine, Instron Co.), five dumbbell-shaped specimens are produced according to ASTM D638, and the tensile strength of each of the five specimens is then measured at a speed of 50 mm / min, and the result can be expressed as the average of these values. This is achieved by meeting the requirement of 425 kgf / cm² as measured according to ASTM D638. 2 Or even greater tensile strength, flame-retardant resin compositions can achieve excellent tensile properties. If the tensile strength decreases to less than 425 kgf / cm², the flame-retardant resin composition can achieve even better tensile properties. 2 If this is not the case, the tensile properties will deteriorate.

[0082] Simultaneously, the flame-retardant resin composition can possess an impact strength of 2.1 kgf‧cm / cm or greater, 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 cantilever beam). There are no particular limitations on the examples of specimens, equipment, and conditions used for measuring impact strength, and the ASTM D256 method and conventionally known methods for measuring the impact strength of resin-molded products can be applied without restriction. The flame-retardant resin composition achieves excellent impact properties by meeting an impact strength of 2.1 kgf‧cm / cm or greater as measured at 23°C according to ASTM D256 (1 / 8-inch, notched cantilever beam). If the impact strength decreases to less than 2.1 kgf‧cm / cm, the impact properties deteriorate.

[0083] Meanwhile, according to another embodiment of the present invention, a flame-retardant product comprising a flame-retardant resin composition of another embodiment can be provided.

[0084] The content related to the flame-retardant resin composition includes the above details regarding other embodiments.

[0085] Flame-retardant products may contain flame-retardant resin compositions or molded products thereof according to other embodiments. The flame-retardant resin composition may be applied directly to the product to form a flame-retardant coating, or it may be applied to components constituting the product to introduce it into the product.

[0086] The specific shape or size of the molded product can vary depending on its intended application, and there are no particular limitations on examples. There are no limitations on examples of molding methods, and molding methods widely known in the field of resin compositions can be applied without restriction. For example, depending on its application, the molded product can be obtained by molding the flame-retardant resin composition via various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, and profile extrusion processes, and by using post-processing methods of the flame-retardant resin composition such as thermoforming.

[0087] There are no particular restrictions on the types of products that can be included, for example, electrical / electronic products and automotive parts.

[0088] Beneficial effects

[0089] According to this disclosure, novel phosphorus-based flame retardant compounds having structures capable of improving the flame retardant and mechanical properties of polymer resins, as well as flame retardant resin compositions and flame retardant products using the same, can be provided. Detailed Implementation

[0090] The invention will be described in more detail in the following embodiments. However, the following embodiments are merely illustrative examples of this disclosure, and the content of this disclosure is not limited to the following embodiments.

[0091] <Preparation Examples 1 to 6: Preparation of Flame Retardant Compounds>

[0092] Preparation Example 1

[0093] The compound represented by chemical formula 1-1 is synthesized by the reaction shown in [reaction formula 1] below.

[0094] [Reaction Formula 1]

[0095]

[0096] Compound L-1 and diethylphosphonic acid (compound M-1) were added to the reactor in a 1:2 molar ratio as reactants, and NaOH as a base was dissolved in water at room temperature with stirring. Then, Al2(SO4)3 was added as an aluminum salt, and the reaction was carried out by raising the temperature to 100°C and stirring for 12 hours.

[0097] The solid was separated by vacuum filtration using a suction device, and the product was further washed twice with water and acetone, and purified. The solid product was transferred to a glass vial, placed in a vacuum oven, and dried overnight to obtain compound 1-1. (Yield: 90%)

[0098] [Chemical Formula 1-1]

[0099]

[0100] Preparation Example 2

[0101] The compounds represented by chemical formulas 1-2 are synthesized by the reaction shown in [reaction formula 2] below.

[0102] [Reaction 2]

[0103]

[0104] The compound represented by chemical formula 1-2 was synthesized in the same manner as in Preparation Example 1, except that L-2 was used as the reactant instead of L-1 (molar ratio 1:1). (Yield: 92%)

[0105] [Chemical Formula 1-2]

[0106]

[0107] Preparation Example 3

[0108] [Reaction 3]

[0109] The compounds represented by chemical formulas 1-3 are synthesized by the reaction shown in [reaction formula 3] below.

[0110]

[0111] Compounds represented by chemical formulas 1-3 were synthesized in the same manner as in Preparation Example 1, except that L-3 was used instead of L-1 as a reactant and M-2 was used instead of M-1 (molar ratio 1:1). (Yield: 88%)

[0112] [Chemical Formulas 1-3]

[0113]

[0114] Preparation Example 4

[0115] [Reaction 4]

[0116] The compounds represented by chemical formulas 1-4 are synthesized by the reaction shown in [reaction formula 4] below.

[0117]

[0118] Compounds represented by chemical formulas 1-4 were synthesized in the same manner as in Preparation Example 1, except that L-4 was used as the reactant instead of L-1 and M-3 was used instead of M-1 (molar ratio 1:1). (Yield: 91%)

[0119] [Chemical Formulas 1-4]

[0120]

[0121] Preparation Example 5

[0122] [Reaction 5]

[0123]

[0124] Compounds represented by chemical formulas 1-5 were synthesized in the same manner as in Preparation Example 1, except that L-5 was used as the reactant instead of L-1 (molar ratio 1:2). (Yield: 95%)

[0125] [Chemical Formulas 1-5]

[0126]

[0127] Preparation Example 6

[0128] [Reaction Formula 6]

[0129]

[0130] Compounds represented by chemical formulas 1-6 were synthesized in the same manner as in Preparation Example 1, except that L-6 was used as the reactant instead of L-1 (molar ratio 2:1). (Yield: 93%)

[0131] [Chemical Formulas 1-6]

[0132]

[0133] <Comparative Preparation Example 1: Preparation of Flame Retardant Compounds>

[0134] Comparative Preparation Example 1

[0135] The following compound A-1 was used in Comparative Preparation Example 1.

[0136] [Compound A-1]

[0137]

[0138] <Examples 1 to 6: Preparation of Flame Retardant Resin Compositions>

[0139] Flame-retardant resin compositions are prepared using compounds of chemical formulas 1-1 to 1-6 as phosphorus-based flame retardants.

[0140] Based on the composition in Table 1 below, and the total weight of solids in the flame-retardant resin composition, 85% by weight of thermoplastic resin and 15% by weight of phosphorus-based flame retardant were mixed for 5 to 20 minutes and then added to an extruder. The mixture was melted and extruded at a barrel temperature of 240°C and a stirring speed of 200 rpm to prepare granules. The prepared granules were dried at 90°C for one day and then injection molded at 240°C to prepare specimens for physical property measurements.

[0141] [Table 1]

[0142]

[0143] <Comparative Example 1: Preparation of Flame Retardant Resin Composition>

[0144] Comparative Example 1

[0145] As shown in Table 1, the resin composition was prepared in the same manner as in Example 1, except that compound A-1 obtained in Comparative Preparation Example 1 was used instead of phosphorus-based flame retardant compound 1-1 obtained in Preparation Example 1.

[0146] <Experimental Example: Measurement of the Physical Properties of Flame-Retardant Resin Compositions>

[0147] The properties of the flame-retardant resin compositions obtained in the examples and comparative examples were measured using the following methods, and the results are shown in Table 3.

[0148] 1. Flame retardancy

[0149] The flame retardant components obtained in the examples and comparative examples were mixed with polymer granules and optional additives, and then blended using a twin-screw extruder at a temperature of 230°C to 260°C or at a temperature of 260°C to 280°C. The homogenized polymer filaments were stretched, cooled in a water bath, and then granulated.

[0150] After thorough drying, the molded composition is processed in an injection molding machine at a melt temperature of 240°C to 270°C or a melt temperature of 260°C to 290°C to obtain a specimen. Flame retardancy is evaluated according to the UL-94 test standard using specimens with dimensions of 1.6 mm thickness, 12.7 mm width, and 127 mm length.

[0151] Specifically, after applying a 20 mm high flame to the specimen for 10 seconds, the burning time (t1) of the specimen was measured, and the burning pattern was recorded. Subsequently, after the first flame contact, when combustion was complete, the specimen was brought into contact with the flame again for 10 seconds, and the burning time (t2) and spark formation time (flameless combustion time, t3) of the specimen were measured, and the burning pattern was recorded. The same procedure was applied to five specimens, and then they were evaluated based on the criteria in Table 2 below.

[0152] [Table 2]

[0153]

[0154] 2. Properties other than flame retardancy

[0155] (1) Tensile strength: It was measured according to ASTM D638. Specifically, five dumbbell-shaped specimens were prepared according to ASTM D638 using a UTM-5566 (Universal Testing Machine, Instron Co.), and the tensile strength of each of the five specimens was measured at a speed of 50 mm / min. The results are expressed as the average of these values.

[0156] (2) Room temperature impact strength of cantilever beam: It is measured at 23°C according to ASTM D256 (1 / 8 inch, notched cantilever beam).

[0157] [Table 3]

[0158] Experimental results

[0159]

[0160] As shown in Table 3, it was determined that, compared to Comparative Example 1, the flame retardant compound containing phosphorus-based compounds (which are composed of substituents of Formula 1) was superior. - (Metal coordination complexes of ligands), the flame-retardant resin compositions obtained in Examples 1 to 6 exhibit excellent flame-retardant properties, wherein the UL rating is VO or V1, and at the same time, both their tensile strength and impact strength are high.

[0161] On the other hand, Comparative Example 1 contains a conventional reactive flame retardant compound that does not contain an x-ligand consisting of a substituent of Formula 1. Although it exhibits a UL rating of VO, it shows that its tensile strength and impact strength are inferior to those of the Examples.

Claims

1. A flame-retardant compound represented by the following chemical formula 1: [Chemical Formula 1] in, In 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 may be the same as or different from each other, and each may independently be hydrogen, hydroxyl, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R3 and R4 may be the same as or different from each other, and each is independently a substituted or unsubstituted linear or branched alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl. R7 is hydrogen or a substituted or unsubstituted alkyl group. M is selected from one or more metal ions and ammonium ions. n, m, x, and y may be the same or different from each other, and each is an independent integer from 1 to 5.

2. The flame retardant compound according to claim 1, wherein in said chemical formula 1: R1 is a substituted or unsubstituted linear or branched alkylene, O, or NR7. R2, R5, and R6 may be the same as or different from each other, and each may independently be a substituted or unsubstituted linear or branched alkyl group, or a substituted or unsubstituted aryl group. R3 and R4 may be the same as or different from each other, and each is independently a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted aryl group, and R7 is hydrogen or a substituted or unsubstituted alkyl group.

3. The flame retardant compound according to claim 1, wherein in said 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 may be the same as 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. R3 and R4 may be the same as 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.

4. The flame retardant compound according to claim 1, The M is selected from one or more of Mg ions, Ca ions, Al ions, Sb ions, Sn ions, Ge ions, Ti ions, Zn ions, Fe ions, Zr ions, Ce ions, Bi ions, Sr ions, Mn ions, Li ions, Na ions, K ions, and ammonium ions.

5. The flame retardant compound according to claim 4, The M is selected from one or more of Al ions, Zn ions, Mg ions, Ca ions and ammonium ions.

6. The flame retardant compound according to claim 1, The flame retardant compound represented by Chemical Formula 1 is a coordination compound between a ligand and a central metal element M, wherein the ligand comprises one or more of a first ligand selected from those represented by Chemical Formula 2 and one or more of a second ligand selected from those represented by Chemical Formula 3. [Chemical Formula 2] [Chemical Formula 3] in, In chemical formulas 2 and 3, the definitions of R1 to R6, x, y, n, and m are the same as those described in claim 1.

7. The flame retardant compound according to claim 1, wherein the flame retardant compound represented by said chemical formula 1 comprises compounds selected from any of the following structural formulas: 。 8. A flame-retardant resin composition comprising the flame-retardant compound according to claim 1; and an adhesive resin.

9. The flame-retardant resin composition according to claim 8, The adhesive resin mentioned above includes polyester or polyamide.

10. The flame-retardant resin composition according to claim 8, The content of the flame retardant compound is from 1% 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 according to claim 8.

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