Flame retardant composition, flame retardant resin composition, and molded article

Abstract

Provided are a flame retardant composition having excellent flame retardancy and an excellent balance between dust suppression and powder flowability, a flame retardant resin composition using the same, and a molded article thereof. A flame retardant composition comprising one or more phosphate compounds represented by the general formula (1) or (2). The bulk density of the flame retardant composition is expressed as d (g / cm 3 ), the cumulative 10% particle size in the volume-based particle size distribution of the flame retardant composition is recorded as D 10 (μm), and the cumulative 50% particle size in the volume-based particle size distribution of the flame retardant composition is represented by D 50 (μm), d, D 10 and D 50 Satisfy 0.030≤d / (D 50 ‑D 10 )≤0.110.

Description

Technical Field

[0001] The present invention relates to a flame retardant composition having excellent flame retardancy and an excellent balance between dust suppression and powder flowability, a flame retardant resin composition using the same, and a molded article thereof. Background Art

[0002] Synthetic resins, due to their excellent mechanical properties and high convenience, are used in a wide range of fields and are becoming an indispensable raw material in modern life. However, many synthetic resins are flammable, and depending on their intended use, imparting flame retardancy is essential for improving safety. Various methods for imparting flame retardancy to synthetic resins have been proposed. For example, the method described in Patent Document 1 involves adding an intumescent flame retardant to a synthetic resin.

[0003] Furthermore, methods for improving the powder properties and various other characteristics of intumescent flame retardants have been proposed. For example, Patent Document 2 proposes a flame retardant composition that not only exhibits excellent flame retardancy but also suppresses dust generation and has good storage stability. Furthermore, Patent Document 3 proposes a flame retardant composition that not only exhibits excellent flame retardancy but also suppresses dust generation and smoke generation during combustion.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-026935

[0007] Patent Document 2: International Publication No. 2016 / 125612

[0008] Patent Document 3: International Publication No. 2019 / 009340 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] However, excessively suppressing dust generation can lead to a new problem: reduced powder fluidity. Reduced powder fluidity in flame retardant compositions increases the risk of reduced productivity due to clogging within the powder feeder of a processing machine, and performance degradation due to poor dispersion during mixing with a resin composition. Patent Documents 1 to 3 provide no description or suggestion of this issue, suggesting that conventional flame retardant compositions still have room for improvement in achieving both dust suppression and good powder fluidity.

[0011] Therefore, an object of the present invention is to provide a flame retardant composition having excellent flame retardancy and an excellent balance between dust suppression and powder fluidity, a flame retardant resin composition using the same, and a molded article thereof.

[0012] Solution to the problem

[0013] The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that: for a flame retardant composition using a specified phosphate compound, by setting the ratio of the loose bulk density to the particle size distribution range within a specific range, it is possible to achieve both suppression of dust scattering and good powder fluidity on the basis of excellent flame retardancy, and thus the present invention was completed.

[0014] That is, according to the present invention, there is provided a flame retardant composition containing one or more of the phosphate compounds represented by the following general formula (1) or the following general formula (2).

[0015] When the loose bulk density of the aforementioned flame retardant composition is denoted as d (g / cm 3 ), the cumulative 10% particle size in the volume-based particle size distribution of the aforementioned flame retardant composition is denoted as D 10 (μm), and the cumulative 50% particle size in the volume-based particle size distribution of the aforementioned flame retardant composition is denoted as D 50 (μm), d, D 10 and D 50 satisfy the following formula (I).

[0016] 0.030 ≤ d / (D 50 - D 10 ) ≤ 0.110... (I)

[0017]

[0018] In general formula (1), n1 represents a number from 1 to 100; X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A); p represents a number satisfying 0 < p ≤ n1 + 2.

[0019]

[0020] In general formula (1-A), Z 1 and Z 2 each independently represent an arbitrary group selected from the group consisting of -NR 11 R 12 group, hydroxyl group, mercapto group, linear or branched alkyl group having 1 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms, phenyl group, and vinyl group; R 11 and R 12Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group.

[0021]

[0022] In the general formula (2), n2 represents a number from 1 to 100; Y 1 represents [R 21 R 22 N(CH2) m NR 23 R 24 , piperazine or a diamine containing a piperazine ring; R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; m is an integer from 1 to 10; q represents a number satisfying 0 < q ≤ n2 + 2.

[0023] In the flame retardant composition of the present invention, d preferably satisfies the following formula (II).

[0024] 0.20 ≤ d ≤ 0.80…(II)

[0025] The flame retardant composition of the present invention preferably contains the phosphate compound represented by the foregoing general formula (1) where X 1 is melamine.

[0026] In addition, the flame retardant composition of the present invention preferably contains the phosphate compound represented by the foregoing general formula (2) where Y 1 is piperazine.

[0027] Furthermore, the flame retardant composition of the present invention preferably contains the phosphate compound represented by the foregoing general formula (1) where X 1 is ammonia.

[0028] In addition, the flame retardant composition of the present invention further preferably contains the phosphate compound represented by the foregoing general formula (1) where X 1 is melamine and the phosphate compound represented by the foregoing general formula (2) where Y 1 is piperazine.

[0029] In addition, the flame retardant composition of the present invention preferably contains the phosphate compound represented by the foregoing general formula (1) with n1 being 2 and the phosphate compound represented by the foregoing general formula (2) with n2 being 2.

[0030] In addition, according to the present invention, there is provided a flame retardant resin composition containing the above flame retardant composition and a thermoplastic resin.

[0031] In the flame-retardant resin composition of the present invention, the thermoplastic resin preferably contains a polyolefin resin.

[0032] Furthermore, according to the present invention, there is provided a molded article formed by using the above flame-retardant resin composition.

[0033] Effects of the Invention

[0034] According to the present invention, there can be provided a flame-retardant composition having excellent flame retardancy and an excellent balance between dust suppression and powder fluidity, a flame-retardant resin composition using the same, and a molded article thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic explanatory view showing an apparatus for evaluating the dust scattering property in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0036] Hereinafter, the present invention will be described in detail according to its preferred embodiments.

[0037] <Flame-Retardant Composition>

[0038] The flame-retardant composition of the present invention contains one or more phosphate compounds represented by the following general formula (1) or the following general formula (2).

[0039]

[0040] In general formula (1), n1 represents a number from 1 to 100; X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A); p represents a number satisfying 0 < p ≤ n1 + 2.

[0041]

[0042] In general formula (1-A), Z 1 and Z 2 each independently represent any group selected from the group consisting of -NR 11 R 12 groups, hydroxyl groups, mercapto groups, linear or branched alkyl groups having 1 to 10 carbon atoms, linear or branched alkoxy groups having 1 to 10 carbon atoms, phenyl groups, and vinyl groups; R 11 and R 12 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group.

[0043]

[0044] In general formula (2), n2 represents a number from 1 to 100; Y 1 represents [R 21 R 22N(CH2) m NR 23 R 24 , piperazine or a diamine containing a piperazine ring; R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms; m is an integer of 1 to 10; q represents a number satisfying 0 < q ≤ n2 + 2.

[0045] As Z in the above general formula (1-A) 1 and Z 2 The linear or branched alkyl group having 1 to 10 carbon atoms shown, examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, decyl and the like. In addition, as Z in the above general formula (1-A) 1 and Z 2 The linear or branched alkoxy group having 1 to 10 carbon atoms shown, examples include groups derived from the above alkyl groups. Further, as Z in the above general formula (1-A) 1 and Z 2 The -NR 11 R 12 group in which R 11 and R 12 each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, examples include the alkyl groups having 1 to 6 carbon atoms among the above-listed alkyl groups.

[0046] As specific examples of the triazine derivative represented by the above general formula (1-A), examples include melamine, methylguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.

[0047] The compound represented by the above general formula (1) may be a single compound, or a mixture of two or more kinds having different degrees of condensation or salt species. Among them, it is preferably a phosphate compound represented by the above general formula (1) containing X 1 as melamine and X 1One or more phosphate compounds represented by the general formula (1) above, wherein n1 is ammonia. Furthermore, the phosphate compound preferably includes a pyrophosphate represented by the general formula (1) above, wherein n1 is 2. When the phosphate compounds are used as a mixture, a higher proportion of the pyrophosphate represented by the general formula (1) above, wherein n1 is 2, is more preferred. Thus, heat resistance can be stably improved.

[0048] In the above general formula (2), Y 1 The compounds shown in FIG. 1 include [R 21 R 22 N(CH2) m NR 23 R 24 〕, piperazine or a diamine containing a piperazine ring. 21 ~R 24 They may be the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0049] As the above R 21 ~R 24 The linear or branched alkyl group having 1 to 5 carbon atoms shown in FIG. 1 includes, for example, the above-mentioned Z 1 and Z 2 Among the specific examples of the alkyl group shown in the figure, the alkyl group has 1 to 5 carbon atoms.

[0050] Examples of the piperazine ring-containing diamine include compounds in which one or more of the 2-, 3-, 5-, and 6-positions of piperazine are substituted with an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms); and compounds in which the amino group at the 1- and / or 4-positions of piperazine is substituted with an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms).

[0051] As Y in the above general formula (2) 1 Specific examples of the compound include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, and 1,4-bis(3-aminopropyl)piperazine.

[0052] The compound represented by the general formula (2) may be a single compound or a mixture of two or more compounds having different condensation degrees or salt types. 1 The phosphate compound represented by the general formula (2) is piperazine. Furthermore, the phosphate compound preferably includes a pyrophosphate represented by the general formula (2) wherein n2 is 2. When the phosphate compound is used as a mixture, a higher content of the pyrophosphate wherein n2 is 2 is more preferred. Thus, heat resistance can be stably improved.

[0053] As a method for producing the above-mentioned phosphate compounds, for example, a salt of a phosphoric acid and melamine, such as melamine pyrophosphate, can be obtained by mixing sodium pyrophosphate and melamine in an arbitrary ratio, adding hydrochloric acid to react, and neutralizing with sodium hydroxide. Alternatively, for example, a salt of a phosphoric acid and piperazine can be easily obtained as a water-insoluble precipitate by reacting the phosphoric acid and piperazine in an arbitrary ratio in water or a methanol aqueous solution. In this case, the composition of the raw phosphoric acid is not particularly limited. Furthermore, a phosphate compound in which n1 or n2 in the above-mentioned general formula (1) or the above-mentioned general formula (2) is 2 or more can be obtained by heating and condensing an orthophosphate in which n1 or n2 is 1.

[0054] The above-mentioned phosphate compounds can be obtained by the above-mentioned operation. They can be used alone or in combination of two or more. The flame retardant composition containing such phosphate compounds can impart excellent flame retardancy to resin materials.

[0055] From the viewpoint of flame retardancy, the flame retardant composition of the present invention preferably contains both the phosphate compound represented by the above-mentioned general formula (1) and the phosphate compound represented by the above-mentioned general formula (2).

[0056] It is particularly preferred to use X in combination 1 The phosphate compound represented by the general formula (1) above of melamine and Y 1 The phosphate compound represented by the above general formula (2) is piperazine. In addition, it is also preferable to use the phosphate compound represented by the above general formula (1) in which n1 is 2 and the phosphate compound represented by the above general formula (2) in which n2 is 2 in combination.

[0057] From the viewpoint of flame retardancy, when the flame retardant composition of the present invention contains both the phosphate compound represented by the general formula (1) and the phosphate compound represented by the general formula (2), the content ratio of the former to the latter is preferably 20:80 to 60:40, more preferably 25:75 to 55:45, and even more preferably 30:70 to 50:50.

[0058] Furthermore, as described above, the present inventors have found through their studies that the bulk density of the flame retardant composition affects the scattering properties of dust.

[0059] It's generally assumed that a lower bulk density of a powder results in higher dust scattering. However, the present inventors' research surprisingly revealed that the flame retardant composition of the present invention, which contains the aforementioned specific phosphate compound, exhibits the opposite effect. Specifically, they discovered that a higher bulk density of the flame retardant composition increases its dust scattering.

[0060] Based on this understanding, the present inventors conducted further in-depth research and discovered that by setting the ratio of the bulk density to the particle size distribution width of the flame retardant composition to a value above and below a specified value, it is possible to achieve both dust suppression and good powder flowability of the flame retardant composition. In other words, simply suppressing the dust dispersion of the powder may adversely affect the powder flowability. However, the present inventors' research results have revealed that by appropriately setting the ratio of the bulk density to the particle size distribution width, it is possible to achieve both dust suppression and good powder flowability.

[0061] Therefore, the flame retardant composition of the present invention suppresses dust dispersion, thereby preventing deterioration of the working environment caused by dust. Furthermore, the flame retardant composition of the present invention exhibits excellent powder flowability, thereby less likely to adversely affect productivity and dispersibility when mixed with resin materials.

[0062] The flame retardant composition of the present invention has a bulk density d (g / cm 3 ), the cumulative 10% particle size in the volume-based particle size distribution is recorded as D 10 (μm), the cumulative 50% particle size in the volume-based particle size distribution is recorded as D 50 (μm), d, D 10 and D 50 Satisfies the following formula (I).

[0063] 0.030≤d / (D 50 -D 10 )≤0.110…(I)

[0064] In the above formula (I), d / (D 50 -D 10 ) is 0.030 or more, preferably 0.035 or more, more preferably 0.040 or more. This can improve the fluidity of the powder. On the other hand, in the above formula (I), d / (D 50 -D 10The upper limit of ) is 0.110 or less, preferably 0.107 or less, and more preferably 0.103 or less. This can suppress excessive dust scattering.

[0065] Here, the bulk density d refers to the packing density of the powder when it is allowed to fall naturally. 3 A cylindrical container was filled with a suitable amount of powder composition by dropping it from the upper opening of the container, and the filling mass (g) and capacity (cm 3 ) reading, calculate the capacity per unit (cm 3 The bulk density can be measured using a commercially available powder property measuring device.

[0066] In addition, regarding the cumulative 10% particle size D in the volume-based particle size distribution of the flame retardant composition, 10 and cumulative 50% particle size D 50 For example, the flame retardant composition is dispersed in methanol and then subjected to ultrasonic treatment, and the dispersion is measured using a laser diffraction / scattering particle size distribution analyzer to determine the particle size distribution.

[0067] In the flame retardant composition of the present invention, the value of the bulk density d preferably satisfies the following formula (II).

[0068] 0.20≤d≤0.80…(II)

[0069] In the above formula (II), the lower limit of d is 0.20 or greater, preferably 0.25 or greater, and more preferably 0.30 or greater. This can improve powder flowability. On the other hand, the upper limit of d is 0.80 or less, preferably 0.70 or less, more preferably 0.60 or less, even more preferably 0.55 or less, and particularly preferably 0.50 or less. This can suppress excessive dust dispersion.

[0070] The above-mentioned bulk density d, cumulative 10% particle size D 10 and cumulative 50% particle size D 50 This can be controlled by, for example, appropriately selecting a preparation method such as pulverization or classification. 10 and D 50 The factors for setting the desired numerical range include, for example, appropriate selection of pulverization conditions such as pulverization method and pulverization time, classification conditions such as cutting of coarse particles, and blending conditions. 10 and D 50 The surface treatment can also be controlled by the presence or absence of surface treatment and the appropriate selection of a surface treatment agent. Examples of such surface treatment agents include the surface treatment agents described below, dust suppressants, lubricants, and the like.

[0071] Examples of the pulverizing means used for the pulverization include mortars, ball mills, rod mills, tube mills, conical ball mills, vibrating ball mills, high-speed rocking ball mills, roller mills, pin mills, hammer mills, attritors, jet mills, ejectors, ultrafine grinding mills, nano high-pressure homogenizers, Mager mills, micro-pulverizers, colloid mills, Première colloid mills, micro-powder mills, Chalotte colloid mills, rotary cutters, dry media agitation mills, impact-type ultrafine pulverizers, planetary mills, bead mills, micro-bead mills, attritors, and crushing rollers. These pulverizing means may be used alone or in combination of two or more.

[0072] Examples of the classification method include dry classification such as sieving classification, inertial classification, and centrifugal classification, and wet classification such as sedimentation classification. A pulverizer with a built-in classification function can be used to simultaneously perform pulverization and classification.

[0073] When the flame retardant composition of the present invention is a mixture of multiple components, the components may be mixed after undergoing a preparation process such as pulverization and classification, or the components may be mixed and then subjected to a preparation process such as pulverization and classification.

[0074] The flame retardant composition of the present invention may contain an auxiliary agent.

[0075] Examples of the auxiliary agents include flame retardant auxiliary agents, anti-dripping auxiliary agents, and processing auxiliary agents.

[0076] The flame retardant auxiliary agent may include a metal oxide or a polyol compound, thereby improving the flame retardancy of the resin.

[0077] Examples of the metal oxides include titanium oxide, zinc oxide, calcium oxide, magnesium oxide, zirconium oxide, barium oxide, tin dioxide, lead dioxide, antimony oxide, molybdenum oxide, and cadmium oxide. These can be used alone or in combination of two or more. This can improve the flame retardancy of the resin. Furthermore, aggregation in the powdery or particulate flame retardant composition can be suppressed. It should be noted that, among the metal oxides, zinc oxide is preferred from the perspective of flame retardancy.

[0078] The zinc oxide may or may not be surface-treated. Specifically, commercially available zinc oxides such as zinc oxide type 1 (manufactured by Mitsui Kinzoku Industries, Ltd.), partially coated zinc oxide (manufactured by Mitsui Kinzoku Industries, Ltd.), NANOFINE 50 (ultrafine zinc oxide with an average particle size of 0.02 μm: manufactured by Sakai Chemical Industries, Ltd.), and NANOFINE K (ultrafine zinc oxide coated with zinc silicate with an average particle size of 0.02 μm: manufactured by Sakai Chemical Industries, Ltd.) can be used.

[0079] The polyol compound is a compound having multiple hydroxyl groups bonded thereto, and examples thereof include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl)isocyanurate (THEIC), polyethylene glycol, glycerol, diglycerol, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, and lactose. Among these polyol compounds, one or more compounds selected from the group consisting of pentaerythritol, such as dipentaerythritol, tripentaerythritol, and polypentaerythritol, and condensates of pentaerythritol are preferred. Dipentaerythritol and condensates of pentaerythritol are particularly preferred, and dipentaerythritol is most preferred. Furthermore, THEIC and sorbitol can also be suitably used. These may be used alone or in combination of two or more.

[0080] Examples of the anti-dripping agent include layered silicates, fluorine-based anti-dripping agents, and silicone rubbers, which can suppress dripping of the resin during combustion.

[0081] The above-mentioned layered silicate is a layered silicate mineral and can be either natural or synthetic, without particular limitation. Examples of the above-mentioned layered silicate include montmorillonite, saponite, hectorite, beidellite, steatite, chlorite and other montmorillonite clay minerals; vermiculite, halloysite, swelling mica, talc and the like. These can be used alone or in combination of two or more. Among the above-mentioned layered silicates, saponite or talc is preferred from the perspective of anti-dripping, and talc is particularly preferred from the perspective of economic efficiency such as price.

[0082] The layered silicate may have cations between layers. The cations may be metal ions, some or all of which may be cations other than metal ions, such as organic cations, (quaternary) ammonium cations, and phosphonium cations.

[0083] Examples of the metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, lithium ions, nickel ions, copper ions, and zinc ions.

[0084] Examples of the organic cations or quaternary ammonium cations include lauryltrimethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, distearyldimethylammonium cation, dihydrogenated tallow dimethylammonium cation, and distearyldibenzylammonium cation. These may be used alone or in combination of two or more.

[0085] Specific examples of the fluorine-based anti-drip aid include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene; perfluoromethanesulfonic acid sodium salt, perfluoro-n-butanesulfonic acid potassium salt, perfluoro-tert-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, and perfluoroalkanesulfonic acid alkali metal salts or perfluoroalkanesulfonic acid alkaline earth metal salts. Among them, polytetrafluoroethylene is preferred from the perspective of anti-drip properties. These can be used alone or in combination of two or more.

[0086] The processing aid may be appropriately selected from known processing aids, and may include an acrylic processing aid.

[0087] Examples of the acrylic processing aid include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above-mentioned alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above-mentioned alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; and copolymers of the above-mentioned alkyl methacrylates with vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

[0088] The flame retardant composition may include a surface treatment agent.

[0089] Examples of the surface treatment agent include silicone oil and silane coupling agents. The use of silicone oil can improve the anti-aggregation and storage stability of the powdered flame retardant composition and its dispersibility in synthetic resins. Furthermore, water resistance can be improved.

[0090] As the silicone oil, any known silicone oil having a polysiloxane skeleton can be used without particular limitation. The silicone oil can be a polymer having a straight-chain polysiloxane skeleton, or a polysiloxane in which all side chains are methyl groups, a portion of the side chains may have phenyl groups, or a portion of the side chains may have hydrogen.

[0091] Examples of silicone oils include dimethyl silicone oil in which the side chains and terminals of the polysiloxane are all methyl groups, methylphenyl silicone oil in which the side chains and terminals of the polysiloxane are all methyl groups and a portion of the side chains are phenyl groups, methylhydrogen silicone oil in which the side chains and terminals of the polysiloxane are all methyl groups and a portion of the side chains are hydrogen groups, and copolymers thereof. Some of these silicone oils may be modified by epoxy modification, amino modification, carboxyl modification, etc. These may be used alone or in combination of two or more.

[0092] Among the silicone oils, dimethyl silicone oil and methyl hydrogen silicone oil are preferred, and methyl hydrogen silicone oil is more preferred, from the viewpoint of preventing aggregation of the powdered flame retardant composition, improving storage stability, and improving dispersibility in synthetic resins.

[0093] Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltri(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane, and p-phenylenedimethoxysilane. Examples of the silane coupling agent including an acryl group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. Examples of the silane coupling agent including a methacryl group include 3-methacryloxypropylmethyldimethoxysilane and 3-methyl Examples of the silane coupling agent having an epoxy group include acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and methacryloxyoctyltrimethoxysilane. Examples of the silane coupling agent having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane. Examples of the silane coupling agent having an amino group include N-2-(aminoethyl) Silane coupling agents having an isocyanurate group include 3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Examples of silane coupling agents having an isocyanurate group include tris(trimethoxysilylpropyl)isocyanurate, and examples of silane coupling agents having an isocyanurate group include tris(trimethoxysilylpropyl)isocyanurate. Examples of silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Examples of silane coupling agents having a urea group include 3-ureapropyltrimethoxysilane and 3-ureapropyltriethoxysilane. Examples of silane coupling agents having a sulfide group include bis(triethoxysilylpropyl)tetrasulfide. Examples of silane coupling agents having a thioester group include 3-octanoylthio-1-propyltriethoxysilane. Examples of silane coupling agents having an isocyanate group include 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane. These may be used alone or in combination of two or more.

[0094] Among these silane coupling agents, from the viewpoint of improving flame retardancy and handling properties, preventing aggregation of the powdered flame retardant composition, and improving storage stability, silane coupling agents having an epoxy group are preferred, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane are more preferred.

[0095] Examples of methods for adding the surface treatment agent include mixing a powdered or particulate flame retardant composition with the surface treatment agent, spray-drying the surface treatment agent, and then adding or mixing it. Alternatively, the surface treatment agent may be added to the flame retardant composition by surface-treating a portion of the components constituting the flame retardant composition.

[0096] The flame retardant composition may contain a dust suppressant.

[0097] Examples of the dust suppressant include aliphatic dicarboxylic acid ether ester compounds and the above-mentioned silane coupling agents.

[0098] The aliphatic dicarboxylic acid ether ester compound may include a compound represented by the following general formula (3). This can suppress dusting of the powdery flame retardant composition. These compounds may be used alone or in combination of two or more.

[0099]

[0100] In the general formula (3), n3 represents an integer of 1 to 3; m3 represents an integer of 2 to 6; R 3 It represents an alkyl group having 1 to 6 carbon atoms.

[0101] In the above general formula (3), R 3 The alkyl group having 1 to 6 carbon atoms may be a straight chain alkyl group or a branched chain alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, and hexyl. 3 From the viewpoint of flame retardancy, particularly handling properties and storage stability, butyl is preferred.

[0102] In the general formula (3), n3 is preferably 2 from the viewpoint of flame retardancy, particularly handling properties and storage stability. Furthermore, in the general formula (3), m3 is preferably 4 from the viewpoint of flame retardancy, particularly handling properties and storage stability.

[0103] The flame retardant composition may include other components within the scope of not damaging the effects of the present invention. As other components, additives commonly used to modify thermoplastic resins may be used, such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization nucleating agents, transparentizing agents, plasticizers, lubricants, other flame retardants other than the phosphate compounds of the present invention, reinforcing materials, crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, anti-precipitation agents, fluorescent agents, mildew inhibitors, bactericides, foaming agents, metal inertizing agents, release agents, pigments, dyes, etc. These may be used alone or in combination of two or more.

[0104] Examples of the antioxidant include phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and other antioxidants.

[0105] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butylphenol), and 2,6-di-tert-butyl-p-cresol. -tert-Butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Methylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), thiodiglycol bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 1,6-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis (3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid) diol Ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. These phenolic antioxidants may be used alone or in combination of two or more.

[0106] Examples of the phosphite antioxidant include tris(nonylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidene diphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5 -methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2' -Methylenebis(4,6-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepane-6-yl)oxy]ethyl)amine, phosphite ester of 2-ethyl-2-butylpropanediol and 2,4,6-tri-tert-butylphenol, etc. These phosphite-based antioxidants may be used alone or in combination of two or more.

[0107] Examples of the thioether antioxidant include 3,3'-thiodipropionic acid, alkyl (C12-14) thiopropionate, di(lauryl)-3,3'-thiodipropionate, di(tridecyl)-3,3'-thiodipropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3,3'-thiodipropionate, and laurylstearyl. Thiodipropionate, tetrakis[methylene-3-(dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propionate), 2,2'-thiodiethylenebis(3-aminobutyrate), 4,6-bis(octylthiomethyl)o-cresol, 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-Thiobis(4-methyl-6-tert-butylphenol), 2,2'-thiobis(6-tert-butyl-p-cresol), 2-ethylhexyl-(3,5-di-tert-butyl-4-hydroxybenzyl)thioacetate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(4-methyl-6-tert-butylphenol), 4,4'-[thiobis(methylene)]bis(2-tert-butyl-6-methyl- 1-hydroxybenzyl), bis(4,6-di-tert-butylphenol-2-yl) sulfide, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, 1,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, distearyl disulfide, bis(methyl-4-[3-n-alkyl(C12 / C14)thiopropionyloxy]5-tert-butylphenyl) sulfide, etc. These thioether-based antioxidants may be used alone or in combination of two or more.

[0108] Examples of other antioxidants include nitrone compounds such as N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, and N-octadecyl-α-heptadecylnitrone; 3-arylbenzofuran-2(3H)-ones; 3-(alkoxyphenyl)benzofuran-2-ones; 3-(acyloxyphenyl)benzofuran-2(3H)-ones; and 5-[3-H]-benzo[3-]-ones. Benzofuran compounds such as benzofuran-2(3H)-one, benzofuran-3-(3,4-dimethylphenyl)-benzofuran-2(3H)-one, benzofuran-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, benzofuran-2(3H)-one, benzofuran-3-{4-(2-hydroxyethoxy)phenyl}-benzofuran-2(3H)-one, 6-(2-(4-(5,7-di-tert-2-oxo-2,3-dihydrobenzofuran-3-yl)phenoxy)ethoxy)-6-oxohexyl-6-((6-hydroxyhexanoyl)oxy)hexanoate, and benzofuran-2(3H)-one, can be used alone or in combination of two or more.

[0109] Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)bis(tridecyl)-1,2,3,4-butane Tetracarboxylic acid esters, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)bis(tridecyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1, 5,8,12-Tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-Tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane [(1,2,3,4-Butanetetracarboxylic acid), 2,2-bis(hydroxymethyl)-1,3-propanediol polymer with 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl-4-piperidinyl ester, 1,3-bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,3,4-butanetetracarboxylic acid, 2,2-bis(hydroxymethyl)-1,3-propanediol polymer with 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl-4-piperidinyl ester, 1,3-bis(2,2,6,6-tetramethylpiperidin-4-yl) 2,4-ditidecylbenzene-1,2,3,4-tetracarboxylate, bis(1-octyloxy-2,2,6,[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]), TINUVIN NOR371 manufactured by BASF, etc. These light stabilizers may be used alone or in combination of two or more.

[0110] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl salicylate, resorcinol monohydrate Benzoates such as benzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxalanilides such as 2-ethyl-2'-ethoxyoxalanilide and 2-ethoxy-4'-dodecyloxalanilide; ethyl-α-cyano-β,β-diphenylacrylate, Cyanoacrylates such as methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; triaryl triazines such as 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These ultraviolet absorbers may be used alone or in combination of two or more.

[0111] Examples of the crystal nucleating agent include carboxylic acid metal salts such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; phosphoric acid ester metal salts such as sodium bis(4-tert-butylphenyl)phosphate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate; diphenylmethylene sorbitol, bis(methylphenylmethylene)sorbitol, bis(3,4-dimethylphenylmethylene)sorbitol, bis(p-ethylphenylmethylene)sorbitol, and bis(dimethylphenylmethylene)sorbitol. Polyol derivatives such as sugar alcohols, 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl)methylene)nonanol, 1,3:2,4-bis(p-methylphenylmethylidene)sorbitol, and 1,3:2,4-bis-O-phenylmethylidene-D-sorbitol (diphenylmethylidene sorbitol); and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, and 1,3,5-tris(dimethylisopropylamino)benzene. These crystal nucleating agents may be used alone or in combination of two or more.

[0112] Examples of plasticizers include epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid octyl esters; methacrylate-based plasticizers; polyester-based plasticizers such as polycondensates of dicarboxylic acids and polyols, and polycondensates of polycarboxylic acids and polyols; polyetherester-based plasticizers such as polycondensates of dicarboxylic acids, polyols, and alkylene glycols, polycondensates of dicarboxylic acids, polyols, and arylene glycols, polycondensates of polycarboxylic acids, polyols, and alkylene glycols, and polycondensates of polycarboxylic acids, polyols, and arylene glycols; aliphatic esters such as adipates and succinates; and aromatic esters such as phthalates, terephthalates, trimellitates, pyromellitates, and benzoates. These plasticizers may be used alone or in combination of two or more.

[0113] Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microcrystalline wax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and hydroxy fatty acids; fatty acid amide lubricants such as fatty acid amide and bisfatty acid amide; ester lubricants such as polyol esters of fatty acids such as lower alcohol esters of fatty acids and glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester wax); lubricants such as metal soaps, fatty alcohols, polyols, polyglycols, polyglycerols, partial esters of fatty acids and polyols, partial esters of fatty acids and polyglycols or polyglycerols; silicone oils, mineral oils, and the like. These lubricants may be used alone or in combination of two or more.

[0114] Examples of flame retardants other than the phosphate compounds of the present invention include triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-di(cresyl) phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetra(2,6-dimethylphenyl) phosphate, and ADEKA products under the trade names of "ADK STAB FP-500", "ADK STAB FP-600", "ADK STAB FP-800", and "ADK STAB FP-900". Aromatic phosphates such as FP-900L; phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, and 1-butenyl phenylphosphonate; phosphinates such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; dialkyl phosphinates such as aluminum diethylphosphinate and zinc diethylphosphinate; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and ditolylphosphazene; inorganic phosphorus flame retardants such as red phosphorus; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; brominated bisphenol A epoxy resins, Brominated phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromobenzene), ethylenebis(tetrabromophthalimide), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, brominated styrene, and other brominated flame retardants. These other flame retardants may be used alone or in combination of two or more.

[0115] Examples of antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; anionic antistatic agents such as higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, and higher alcohol ethylene oxide adduct phosphates; nonionic antistatic agents such as polyol fatty acid esters, polyglycol phosphates, and polyoxyethylene alkyl allyl ethers; amphoteric alkyl betaines such as alkyl dimethylaminoacetic acid betaine; and amphoteric antistatic agents such as imidazoline-type amphoteric surfactants. These antistatic agents may be used alone or in combination of two or more.

[0116] As filler, for example talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, mica, silicon dioxide, aluminum oxide, potassium titanate whisker, wollastonite, fibrous basic magnesium sulfate, montmorillonite etc. can be listed out, can suitably select particle diameter (for fibrous, suitably select fiber diameter, fiber length and aspect ratio) to use.These fillers can be used alone a kind, also can be used in combination more than two kinds.In addition, filler can use the material that carries out surface treatment and obtains as required.

[0117] Examples of the pigment include Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153 3, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These pigments may be used alone or in combination of two or more.

[0118] Examples of the dye include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indane dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These dyes may be used alone or in combination of two or more.

[0119] It should be noted that one or more of the above-mentioned auxiliary agents, surface treatment agents, dust suppressants and other components may be blended into the above-mentioned flame retardant composition or into a flame retardant resin composition comprising the above-mentioned flame retardant composition and a thermoplastic resin.

[0120] The flame retardant composition of the present invention can be obtained by mixing one or more of the phosphate compounds represented by the general formula (1) or the general formula (2) with other optional components as needed, provided that the above formula (1) is satisfied. Various mixers can be used for mixing. Heat can be applied during mixing. Usable mixers are not particularly limited, and examples thereof include a drum agitator, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super agitator, and a Nauta agitator.

[0121] When the flame retardant composition obtained by mixing does not satisfy the above formula (I), it can be adjusted so as to satisfy the above formula (I) by adding a surface treatment agent, a dust suppressant, pulverizing with a pulverizer, etc.

[0122] <Flame-retardant resin composition>

[0123] The flame-retardant resin composition of the present invention contains the flame retardant composition and a thermoplastic resin.

[0124] The content of the flame retardant composition is generally 10 to 400 parts by mass, preferably 15 to 200 parts by mass, and more preferably 20 to 70 parts by mass per 100 parts by mass of the thermoplastic resin, thereby sufficiently improving the flame retardancy of the thermoplastic resin.

[0125] Examples of the thermoplastic resin include synthetic resins such as polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins, which may be used alone or in combination of two or more.

[0126] If further examples of the above-mentioned thermoplastic resins are listed, thermoplastic resins such as petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resins, polyimide resins, polysulfones, liquid crystal polymers, and blends thereof can be used.

[0127] In addition, the above-mentioned thermoplastic resin can be a thermoplastic elastomer such as isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, polyamide elastomer, polyurethane elastomer, etc., and they can also be used in combination.

[0128] Specific examples of the thermoplastic resin include, but are not particularly limited to, polyolefin resins such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, α-olefin polymers such as ethylene / propylene block copolymers or random copolymers; thermoplastic linear polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate; polysulfide resins such as polyphenylene sulfide; polylactic acid resins such as polycaprolactone; linear polyamide resins such as polyhexamethylene adipamide; and crystalline polystyrene resins such as syndiotactic polystyrene.

[0129] These thermoplastic resins can be used regardless of their molecular weight, degree of polymerization, density, softening point, proportion of insoluble components in the solvent, degree of stereoregularity, presence or absence of catalyst residues, type of monomers used as raw materials, blending ratio, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc.

[0130] Among these thermoplastic resins, from the viewpoint of imparting excellent flame retardancy, one or more selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof are preferred, polyolefin resins are more preferred, and polypropylene, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene are even more preferred. These are also preferably used in combination with a thermoplastic elastomer.

[0131] The flame retardant resin composition may contain, on the basis of the flame retardant composition, one or more additives selected from the auxiliary agent, surface treatment agent, dust suppressant, and other components as needed. These may be used alone or in combination of two or more.

[0132] The content of the additives in the flame-retardant resin composition (excluding the flame retardant other than the filler and the phosphate compound of the present invention) is, for example, 0.001 to 15 parts by mass, preferably 0.005 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the thermoplastic resin. By setting this numerical range, the effect of the additives can be enhanced.

[0133] When the filler is added to the flame-retardant resin composition, the content of the filler is, for example, 1 to 100 parts by mass, preferably 3 to 80 parts by mass, and more preferably 5 to 50 parts by mass per 100 parts by mass of the thermoplastic resin.

[0134] When a flame retardant other than the phosphate compound of the present invention is added to the flame retardant resin composition, the content thereof is, for example, 1 to 200 parts by mass, preferably 3 to 150 parts by mass, and more preferably 5 to 80 parts by mass per 100 parts by mass of the thermoplastic resin.

[0135] In the flame retardant resin composition, when a polyolefin resin or an olefin elastomer is used as a thermoplastic resin, in order to neutralize the catalyst residue in the resin, the flame retardant resin composition preferably contains a known neutralizing agent within a range that does not impair the effect of the present invention. As the neutralizing agent, for example, fatty acid metal salts such as calcium stearate, lithium stearate, sodium stearate, and magnesium stearate; fatty acid amide compounds such as ethylenebis(stearamide), ethylenebis(12-hydroxystearamide), and stearamide; or inorganic compounds such as hydrotalcite. These neutralizing agents may be used alone or in combination of two or more. The amount of these neutralizing agents used is preferably 0.001 to 3 parts by mass relative to 100 parts by mass of the thermoplastic resin, and more preferably 0.01 to 1 part by mass.

[0136] Next, a method for producing the flame-retardant resin composition will be described.

[0137] The flame retardant resin composition can be obtained by mixing the flame retardant composition with a thermoplastic resin. The additives described above can also be mixed as needed. The additives can be mixed into the flame retardant composition or into a mixture of the flame retardant composition and the thermoplastic resin.

[0138] As a mixing method, commonly used known methods can be directly applied. Examples include methods of mixing the flame retardant composition, thermoplastic resin, and, if necessary, additives using a conventional blender, stirrer, or other mixer; methods of melt-kneading using an extruder; and methods of mixing with a solvent and performing solution casting.

[0139] The flame-retardant resin composition can be used in various forms, such as pellets, granules, and powders. From the viewpoint of handling, the flame-retardant resin composition is preferably in the form of pellets.

[0140] <molded body>

[0141] The molded article of the present invention is produced using the flame-retardant resin composition. The molded article can be produced by molding the flame-retardant resin composition.

[0142] The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum forming, inflation molding, calendaring, beveling molding, dip molding, foaming, and additive manufacturing. Among them, injection molding, extrusion molding, and blow molding are preferred.

[0143] This makes it possible to produce molded products of various shapes, such as resin plates, sheets, films, and irregularly shaped products.

[0144] Molded articles made using the flame-retardant resin composition can be used in various applications, such as electrical / electronic components, mechanical components, optical equipment, building components, automotive components, and daily necessities. Among them, from the perspective of flame retardancy, they are particularly suitable for electrical / electronic components and building components.

[0145] The flame retardant resin composition and its molded article can be used in a wide range of industrial fields such as electrical / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, furniture, printing, and musical instruments. Specifically, the flame retardant resin composition of the present invention and its molded article can be used in office and office equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, fax machines, ECRs (electronic character receivers), calculators, electronic notepads, cards, brackets, and stationery, home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsus, AV equipment such as TVs, VTRs, digital video cameras, recorders, compact discs, CD players, speakers, and liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, LED sealing materials, wires, cables, transformers, deflection coils, distribution boards, and clocks, and communication equipment.

[0146] The flame-retardant resin composition and its molded article can be used in various fields such as materials for automobiles, vehicles, ships, aircraft, buildings, and houses, such as seats (fillers, outer materials, etc.), belts, ceiling interiors, convertible tops, armrests, door trims, rear luggage trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, shoulder straps, lanyards, wire covering materials, electrical insulating materials, paints, coating materials, covering materials, flooring materials, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, deck materials, wall materials, pillar materials, floor panels, fence materials, frames and molds, door and window profiles, wood veneers, wood panel walls, rooftops, balconies, sound insulation panels, heat insulation panels, window materials, construction materials, civil engineering materials, clothing, curtains, bed sheets, plywood, synthetic fiber boards, cord carpets, doormats, bed sheets, buckets, hoses, containers, glasses, bags, boxes, goggles, skis, rackets, tents, and musical instruments, as well as daily necessities and sporting goods.

[0147] The embodiments of the present invention have been described above, but they are merely illustrative of the present invention, and various configurations other than those described above may be employed. In addition, the present invention is not limited to the above-described embodiments, and the present invention includes modifications and improvements within the scope of achieving the purpose of the present invention.

[0148] Example

[0149] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

[0150] <Manufacturing of Melamine Salt>

[0151] Melamine pyrophosphate is heated and condensed in a solid phase at 220°C for 6 hours to produce a melamine salt containing melamine pyrophosphate as the main component. The melamine salt is used directly without purification. The purity of the melamine pyrophosphate in the melamine salt is 98.5%.

[0152] <Manufacturing of Piperazine Salt>

[0153] Piperazine diphosphate was subjected to a solid-phase heat condensation reaction at 250°C for 1 hour to produce a piperazine salt containing piperazine pyrophosphate as the main component. The piperazine salt was used directly without purification. The purity of the piperazine pyrophosphate in the piperazine salt was 99.0%.

[0154] The purity of the melamine salt and the piperazine salt was measured using an ion chromatograph ICS-2100 (manufactured by Thermo Fisher Scientific, Inc.), a Dionex IonPac AS-19 column (manufactured by Thermo Fisher Scientific, Inc.), and a conductivity detector.

[0155] <Preparation of Composition A1>

[0156] 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) at a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. The mixture was then mixed with 0.3 parts by mass of methyl hydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food blender, and heated to 150°C in an oven. After naturally cooling to room temperature, 0.3 parts by mass of dimethyl silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender to obtain Composition A1.

[0157] <Preparation of Composition A2>

[0158] 35 parts by mass of the melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.), 60 parts by mass of the piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) at a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. 0.3 parts by mass of methyl hydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed using a food blender and heated to 150°C in a heating oven. After cooling naturally to room temperature, 0.3 parts by mass of butyl stearate were mixed using a food blender to obtain Composition A2.

[0159] <Preparation of Composition A3>

[0160] 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) at a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. The mixture was then mixed with 0.3 parts by mass of methyl hydrogen silicone oil (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food blender, and heated to 150°C in a heating oven. After naturally cooling to room temperature, 0.3 parts by mass of dimethyl silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender to obtain Composition A3.

[0161] <Preparation of Composition A4>

[0162] 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) at a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. The mixture was then mixed with 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) using a food blender, and heated to 150°C in a heating oven. After cooling naturally to room temperature, 0.2 parts by mass of bis[2-(2-butoxyethoxy)ethyl adipate] was mixed using a food blender to obtain Composition A4.

[0163] <Preparation of Composition A5>

[0164] 40 parts by mass of the melamine salt and 60 parts by mass of the piperazine salt were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) at a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. The mixture was then mixed with 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food blender, and heated to 150°C in an oven. After naturally cooling to room temperature, 0.2 parts by mass of bis[2-(2-butoxyethoxy)ethyl adipate] was mixed using a food blender to obtain Composition A5.

[0165] <Preparation of Composition A6>

[0166] 40 parts by mass of the melamine salt, 60 parts by mass of the piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. The mixture was mixed with 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food blender, and heated to 150° C. in a heating oven. After naturally cooling to room temperature, 0.2 parts by mass of polyethylene glycol dioctanoate (300) was mixed using a food blender to obtain Composition A6.

[0167] <Preparation of Composition A7>

[0168] 35 parts by mass of the melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.), and 60 parts by mass of the piperazine salt were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. One part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven. After naturally cooling to room temperature, 0.2 parts by mass of polyethylene glycol dioctanoate (300) was mixed using a food blender to obtain Composition A7.

[0169] <Preparation of Composition A8>

[0170] 70 parts by mass of ammonium polyphosphate (Exolit AP422, manufactured by Clariant), 20 parts by mass of poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], 10 parts by mass of melamine cyanurate (MC-4000, manufactured by Nissan Chemical Co., Ltd.), and 0.2 parts by mass of stearic acid were mixed and pulverized using a food blender (for 2 minutes) to obtain Composition A8.

[0171] <Preparation of Composition A9>

[0172] 60 parts by mass of ammonium polyphosphate (Exolit AP422, manufactured by Clariant), 20 parts by mass of aluminum diethylphosphinate (Exolit OP1230, manufactured by Clariant), 20 parts by mass of poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], and 0.2 parts by mass of stearic acid were mixed and pulverized (for 2 minutes) using a food blender to obtain Composition A9.

[0173] <Preparation of Composition A10>

[0174] 60 parts by mass of the piperazine salt and 40 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feed rate of 100 g / h. 0.2 parts by mass of stearic acid were then mixed using a food blender to obtain Composition A10.

[0175] <Preparation of Composition A11>

[0176] 70 parts by mass of ammonium polyphosphate (Exolit AP422, manufactured by Clariant) and 30 parts by mass of melamine cyanurate (MC-4000, manufactured by Nissan Chemical Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 200 g / h. 0.2 parts by mass of stearic acid were then mixed using a food blender to obtain Composition A11.

[0177] <Preparation of Composition B1>

[0178] 40 parts by mass of the above-mentioned melamine salt, 60 parts by mass of the above-mentioned piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 0.3 parts by mass of methyl hydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender and heated to 150° C. in a heating oven to obtain Composition B1.

[0179] <Preparation of Composition B2>

[0180] 35 parts by mass of the above-mentioned melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.), 60 parts by mass of the above-mentioned piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining and Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 0.3 parts by mass of methyl hydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven to obtain Composition B2.

[0181] <Preparation of Composition B3>

[0182] 40 parts by mass of the above-mentioned melamine salt, 60 parts by mass of the above-mentioned piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 0.3 parts by mass of methyl hydrogen silicone oil (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender and heated to 150° C. in a heating oven to obtain Composition B3.

[0183] <Preparation of Composition B4>

[0184] 40 parts by mass of the above-mentioned melamine salt, 60 parts by mass of the above-mentioned piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining and Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven to obtain Composition B4.

[0185] <Preparation of Composition B5>

[0186] 40 parts by mass of the above-mentioned melamine salt and 60 parts by mass of the above-mentioned piperazine salt were pulverized using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender and heated to 150° C. in a heating oven to obtain Composition B5.

[0187] <Preparation of Composition B6>

[0188] 40 parts by mass of the above-mentioned melamine salt, 60 parts by mass of the above-mentioned piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Mining and Smelting Co., Ltd.) were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven to obtain Composition B6.

[0189] <Preparation of Composition B7>

[0190] 35 parts by mass of the above-mentioned melamine salt, 5 parts by mass of melamine polyphosphate (PMP100, manufactured by Nissan Chemical Co., Ltd.), and 60 parts by mass of the above-mentioned piperazine salt were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 100 g / h. 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven to obtain Composition B7.

[0191] <Preparation of Composition B8>

[0192] 100 parts by mass of composition A3 and 3 parts by mass of process oil (DIANA PROCESS OIL PW-90, manufactured by Idemitsu Kosan Co., Ltd.) were mixed using a food blender to obtain composition B8.

[0193] <Preparation of Composition B9>

[0194] 40 parts by mass of the melamine salt and 60 parts by mass of the piperazine salt were ground using a food blender for 2 minutes, mixed with 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) using a food blender, and heated to 150°C in an oven. After naturally cooling to room temperature, 0.3 parts by mass of bis[2-(2-butoxyethoxy)ethyl adipate] was mixed using a food blender to obtain Composition B9.

[0195] <Preparation of Composition B10>

[0196] 100 parts by mass of composition B1 were ground using a small jet mill (CO-JET SYSTEM α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a P nozzle pressure of 0.5 to 0.7 MPa, a G nozzle pressure of 0.5 to 0.65 MPa, and a sample feeding rate of 50 g / h. 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila-Ace S530, manufactured by JNC Corporation) was mixed using a food blender, and the mixture was heated to 150° C. in a heating oven to obtain composition B10.

[0197] The flame retardant composition obtained by the above operation was measured for the following measurement items. The measurement results and the values ​​calculated based on the measurement results and formula (I) are shown in Tables 1 to 3.

[0198] <Determination of bulk density>

[0199] A powder property evaluation device (Multi-function Tester MT-02, manufactured by Seishin Enterprise Co., Ltd.) was used, and a 5 cm diameter, 100 cm volume 3 The cylindrical container was used to measure the bulk density of the flame retardant composition.

[0200] Fill the container lightly with the sample until a peak is formed, level the excess sample above the container surface, and measure the weight of the sample loosely filled in the container. At this time, the weight of the sample loosely filled in the container (g) ÷ 100 (cm 3 ) to calculate the bulk density (g / cm 3 ).

[0201] <Measurement of Particle Size Distribution>

[0202] Cumulative 10% particle size D 10 and cumulative 50% particle size D 50The flame retardant composition was added to methanol and mixed to obtain a solution, which was dispersed by ultrasonic waves. The solution was then measured using a laser diffraction / scattering particle size distribution analyzer (MICROTRAC MT3000II, manufactured by MICROTRAC BEL) under wet conditions.

[0203] The flame retardant compositions thus obtained were evaluated for the following evaluation items. The evaluation results are shown in Tables 1 to 3.

[0204] <Evaluation of Dust Dispersion Properties>

[0205] like Figure 1 As shown, a transparent acrylic tube 10 (outer diameter: 110 mm, inner diameter: 98 mm, length: 500 mm) with only one side open is erected in a manner that the upper part becomes an opening, and the three sides are surrounded by black acrylic plates 11. 10 g of the flame retardant composition obtained above is weighed and allowed to fall freely from the opening at the upper end of the tube 10, and the condition of the flying dust is photographed with a digital camera. Based on the video taken, the state 5 seconds after the powder contacts the bottom surface is read as an image, and the brightness defined by the HLS color space of the portion 12 near the lower end of the tube at 150 mm is extracted from the image. In addition, the brightness when a standard white plate (X94.62, Y99.79, Z106.92 (SCI method)) is set in portion 12 and the brightness before the flame retardant composition is dropped are also extracted. The degree of dust scattering is calculated according to the following formula (III).

[0206]

[0207] In formula (III), (sample) represents the brightness of portion 12 when the flame retardant composition is dropped, (white) represents the brightness of portion 12 when a standard white plate is placed on portion 12, and (black) represents the brightness of portion 12 before the flame retardant composition is dropped.

[0208] The smaller the value calculated using formula (III), the lower the dust dispersibility of the flame retardant composition. It should be noted that a value of 30 or greater indicates that dust may adversely affect the working environment when supplying the flame retardant composition to a mixer or processing machine. These values ​​are shown in Tables 1 to 3 as dust dispersibility evaluation values.

[0209] <Evaluation of the angle of repose>

[0210] The flame retardant composition is poured into a disk using a funnel and deposited on the disk. The angle at which the disk remains stable without spontaneously collapsing is measured as the angle of repose (°). The lower the value, the better the flowability of the flame retardant composition.

[0211] If the angle of repose is 60° or more, clogging is likely to occur in a hopper or a feeder during processing of the flame retardant composition, which is not preferable.

[0212] <Preparation of Test Specimens for Flame Retardancy Evaluation>

[0213] A flame-retardant resin composition was prepared by blending 0.1 parts by mass of calcium stearate (neutralizer), 0.1 parts by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (phenolic antioxidant), and 0.1 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite (phosphorus antioxidant) into 100 parts by mass of polypropylene (melt flow rate (according to JIS K7210, load 2.16 kg, temperature 230°C) = 14 g / 10 min). Then, 54 parts by mass of the flame retardant composition (A1 to A11, B1 to B10) was blended into the polypropylene resin composition to obtain a flame-retardant resin composition. The obtained flame-retardant resin composition was melt-kneaded using a twin-screw extruder (TEX28V, manufactured by Nippon Steel Works, Ltd.) at a barrel temperature of 200 to 230°C and a screw speed of 150 rpm to obtain pellets of the flame-retardant resin composition. The obtained pellets were injection molded using an injection molding machine (EC60NII-1.5A, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 220°C and a mold temperature of 40°C to obtain test pieces of 127 mm×12.7 mm×1.6 mm.

[0214] <Flame Retardancy Evaluation>

[0215] The obtained test piece was used to perform a flame retardancy evaluation test in accordance with the UL-94V standard.

[0216] A test piece measuring 127 mm long, 12.7 mm wide, and 1.6 mm thick was held vertically, with its lower end exposed to a burner flame for 10 seconds. The flame was then removed, and the time it took for the flame on the test piece to disappear was measured. If the flame extinguished, a second 10-second exposure to the flame was initiated, and the same procedure was repeated as the first, with the time it took for the flame to disappear. Furthermore, the cotton beneath the test piece was evaluated for ignition from the falling flame.

[0217] Flammability ratings are determined according to the UL-94V standard, based on factors such as the initial and secondary burning times and whether the cotton ignites. V-0 is the highest flammability rating, and flame retardancy decreases as it progresses to V-1 and V-2. Products that do not meet any of the V-0, V-2, or V-1 ratings are designated as NR.

[0218] [Table 1]

[0219]

[0220] [Table 2]

[0221]

[0222] [Table 3]

[0223]

[0224] Regarding flame retardancy, Examples 1 to 11 and Comparative Examples 1 to 10 were all good.

[0225] On the other hand, in the evaluation of dust scattering properties, Examples 1 to 11 were good, but Comparative Examples 1 to 7 showed values ​​exceeding 30, which were levels that adversely affected the working environment.

[0226] Furthermore, in the evaluation of the angle of repose, Examples 1 to 11 were good, but Comparative Examples 8 to 10 showed values ​​exceeding 60°, indicating poor powder flowability.

[0227] The above-described results indicate that the flame retardant composition of the present invention has good powder fluidity and low dust scattering, and exhibits good flame retardant performance.

[0228] Description of Reference Numerals

[0229] 10 tubes

[0230] 11 Acrylic sheet

[0231] 12 The part about 150mm from the bottom end of the cylinder

Claims

1. A flame retardant composition, characterized in that It contains a phosphate compound represented by the following general formula (1) and the following general formula (2), The flame retardant composition further contains at least one selected from the group consisting of an agent, an aliphatic dicarboxylic acid ether ester, a surface treatment agent, and a lubricant. The surface treatment agent comprises silicone oil, and the silicone oil comprises dimethyl silicone oil and methyl hydrogen silicone oil, The bulk density of the flame retardant composition is expressed as g / cm 3 The unit of d, The cumulative 10% particle size in the volume-based particle size distribution of the flame retardant composition is expressed as D in μm. 10 The cumulative 50% particle size in the volume-based particle size distribution of the flame retardant composition is recorded as D in μm. 50 hour, d、D 10 and D 50 Satisfies the following formula (I), 0.030≤d / (D 50 -D 10 )≤0.110…(I) In general formula (1), n1 represents a number from 1 to 100; X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A); p represents a number satisfying 0 < p ≤ n1 + 2, In the general formula (1-A), Z 1 and Z 2 Each independently represents a member selected from -NR 11 R 12 any group selected from the group consisting of a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group; R 11 and R 12 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group, In general formula (2), n2 represents a number from 1 to 100; Y 1 represents [R 21 R 22 N(CH2) m NR 23 R 24 , piperazine or a diamine containing a piperazine ring; R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; m is an integer from 1 to 10; q represents a number satisfying 0 < q ≤ n2 + 2.

2. The flame retardant composition according to claim 1, wherein d satisfies the following formula (II): 0.20≤d≤0.80…(II).

3. The flame retardant composition according to claim 1 or 2, comprising X 1 The phosphate compound represented by the general formula (1) is melamine.

4. The flame retardant composition according to claim 1 or 2, comprising Y 1 The phosphate compound represented by the general formula (2) is piperazine.

5. The flame retardant composition according to claim 1 or 2, comprising X 1 The phosphate compound represented by the general formula (1) is ammonia.

6. The flame retardant composition according to claim 1 or 2, comprising: X 1 The phosphate compound represented by the general formula (1) is melamine; and Y 1 The phosphate compound represented by the general formula (2) is piperazine.

7. The flame retardant composition according to claim 1 or 2, comprising: The phosphate compound represented by the general formula (1) wherein n1 is 2; and The phosphate compound represented by the general formula (2) wherein n2 is 2.

8. A flame retardant resin composition, characterized in that It contains: The flame retardant composition according to any one of claims 1 to 7; and Thermoplastic resin.

9. The flame retardant resin composition according to claim 8, wherein The thermoplastic resin contains a polyolefin-based resin.

10. A formed body, characterized in that The flame-retardant resin composition according to claim 9 is used.

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