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

Abstract

The present invention provides a flame retardant composition having excellent flame retardancy and an excellent balance of dust suppression and powder fluidity, a flame retardant resin composition using the same, and a molded article thereof. The flame retardant composition contains one or more of phosphate compounds represented by general formula (1) or general formula (2). When the loose bulk density of the flame retardant composition is d (g / cm3), the cumulative 10% particle diameter in the volume-based particle diameter distribution of the flame retardant composition is D10 (㎛), and the cumulative 50% particle diameter is D50 (㎛), d, D10, and D50 satisfy 0.030 ≤ d / (D50-D10) ≤ 0.110.

Description

Technology Field

[0001] The present invention relates to a flame retardant composition having excellent flame retardancy as well as an excellent balance of dust suppression and powder fluidity, a flame retardant resin composition using the same, and a molded article thereof. Background Technology

[0002] Synthetic resins possess excellent mechanical properties and high convenience, so they are used in a wide range of fields and have become indispensable materials in modern life. On the other hand, most synthetic resins are flammable materials, and depending on the application, it is essential to impart flame retardancy to improve safety. Various methods for imparting flame retardancy to synthetic resins have been proposed so far, and for example, as described in Patent Document 1, a method of adding an intumescent flame retardant to a synthetic resin is known.

[0003] In addition, methods to improve powder properties or various other properties of this intumescent flame retardant have been proposed. For example, Patent Document 2 proposes a flame retardant composition that not only possesses excellent flame retardancy but can also suppress dust generation and has good storage stability. In addition, Patent Document 3 proposes a flame retardant composition that not only possesses excellent flame retardancy but can also suppress dust generation and suppress smoke generation during combustion. Prior art literature

[0004] Japanese Patent Publication No. 2003-026935, International Publication No. 2016 / 125612, International Publication No. 2019 / 009340 The problem to be solved

[0005] However, if the generation of dust is excessively suppressed, a new problem arises in which the powder fluidity is reduced. If the powder fluidity of the flame retardant composition is reduced, there is a high risk of reduced productivity due to clogging in the powder supply device of the processing machine, or deterioration of performance due to poor dispersion during mixing in the resin composition. Regarding this, there is neither description nor indication in Patent Documents 1 to 3, and in conventional flame retardant compositions, there was room for improvement regarding the simultaneous suppression of dust scattering and good powder fluidity.

[0006] Accordingly, the objective of the present invention is to provide a flame retardant composition having excellent flame retardancy and an excellent balance of dust suppression and powder fluidity, a flame retardant resin composition using the same, and a molded article thereof. means of solving the problem

[0007] The inventors, having carefully examined the above problem, discovered that in a flame retardant composition using a predetermined phosphate compound, by keeping the ratio of loose bulk density to particle diameter distribution width within a specific range, it is possible to achieve both excellent flame retardancy and suppression of dust scattering and good powder fluidity, and thus completed the present invention.

[0008] That is, according to the present invention, 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),

[0009] The loose bulk density of the above flame retardant composition is d (g / cm³) 3 ), the cumulative 10% particle diameter in the volume-based particle diameter distribution of the flame retardant composition is D 10 (㎛), cumulative 50% particle diameter D 50 When set to (㎛), d, D 10 and D 50 A flame retardant composition satisfying the following formula (I) is provided.

[0010] 0.030≤d / (D 50 -D 10 )≤0.110 … (I)

[0011]

[0012] In general formula (1), n1 represents a number from 1 to 100, and X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p is 0 <p≤n1+2를 만족시키는 수를 나타낸다.

[0013]

[0014] In general formula (1-A), Z 1 and Z 2 is, each independently, -NR 11 R 12 It represents any one group selected from the group consisting of a hydroxyl group, a mercapto group, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group, and R 11 and R 12 Each represents, independently, a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a methylol group.

[0015]

[0016] In the general formula (2), n2 represents a number from 1 to 100, and Y 1 [R 21 R 22 N(CH2) m NR 23 R 24 ], piperazine, or, representing a diamine containing a piperazine ring, and R 21 , R 22 , R 23 and R 24 Each independently represents a straight-chain or branched alkyl group having 1 to 5 hydrogen atoms or carbon atoms, m is an integer from 1 to 10, and q is 0 <q≤n2+2를 만족시키는 수를 나타낸다.

[0017] In the flame retardant composition of the present invention, it is preferable that d satisfies the following formula (II).

[0018] 0.20≤d≤0.80 … (II)

[0019] The flame retardant composition of the present invention is X 1 It is preferable that this melamine contains the phosphate compound represented by the above general formula (1).

[0020] In addition, the flame retardant composition of the present invention is Y 1 It is preferable to contain the phosphate compound represented by the above general formula (2), which is piperazine.

[0021] In addition, the flame retardant composition of the present invention is X 1 It is preferable to contain the above phosphate compound represented by the above general formula (1), which is ammonia.

[0022] In addition, the flame retardant composition of the present invention is X 1 This melamine is the phosphate compound represented by the above general formula (1), and Y 1 It is also desirable to contain the phosphate compound represented by the above general formula (2), which is piperazine.

[0023] In addition, the flame retardant composition of the present invention preferably contains the phosphate compound represented by the general formula (1) where n1 is 2 and the phosphate compound represented by the general formula (2) where n2 is 2.

[0024] In addition, according to the present invention, a flame-retardant resin composition containing the flame-retardant composition and a thermoplastic resin is provided.

[0025] In the flame-retardant resin composition of the present invention, it is preferable that the thermoplastic resin contains a polyolefin-based resin.

[0026] In addition, according to the present invention, a molded article made using the flame-retardant resin composition is provided. Effects of the invention

[0027] According to the present invention, a flame retardant composition having excellent flame retardancy and an excellent balance of dust suppression and powder fluidity, a flame retardant resin composition using the same, and a molded article thereof can be provided. Brief explanation of the drawing

[0028] Figure 1 is an explanatory diagram schematically showing the apparatus used to evaluate dust dispersion in the embodiment. Specific details for implementing the invention

[0029] Hereinafter, the present invention will be described in detail based on its preferred embodiments.

[0030] Flame Retardant Composition

[0031] The flame retardant composition of the present invention contains one or more of the phosphate compounds represented by the following general formula (1) or the following general formula (2).

[0032]

[0033] In general formula (1), n1 represents a number from 1 to 100, and X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p is 0 <p≤n1+2를 만족시키는 수를 나타낸다.

[0034]

[0035] In general formula (1-A), Z 1 and Z 2 is, each independently, -NR 11 R 12 It represents any one group selected from the group consisting of a hydroxyl group, a mercapto group, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group, and R 11 and R 12 Each represents, independently, a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a methylol group.

[0036]

[0037] In the general formula (2), n2 represents a number from 1 to 100, and Y 1 [R 21 R 22 N(CH2) m NR 23 R 24 ], piperazine, or, representing a diamine containing a piperazine ring, and R 21 , R 22 , R 23 and R 24 Each independently represents a straight-chain or branched alkyl group having 1 to 5 hydrogen atoms or carbon atoms, m is an integer from 1 to 10, and q is 0 <q≤n2+2를 만족시키는 수를 나타낸다.

[0038] Z in the above general formula (1-A) 1 and Z 2 Examples of straight-chain or branched alkyl groups having 1 to 10 carbon atoms represented by 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, etc. Additionally, Z in the above general formula (1-A) 1 and Z 2 Examples of straight-chain or branched alkoxy groups having 1 to 10 carbon atoms represented by can be groups derived from the alkyl group. In addition, Z in the general formula (1-A) 1 and Z 2 -NR that can have 11 R 12 R in the energy 11 and R 12 As for the straight-chain or branched alkyl group having 1 to 6 carbon atoms represented by, there are alkyl groups having 1 to 6 carbon atoms among the alkyl groups given as examples above.

[0039] Specific examples of triazine derivatives represented by the above general formula (1-A) include melamine, acetoguanamin, benzoguanamine, acrylguanamin, 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, Examples include 2-amino-4,6-dimercapto-1,3,5-triazine.

[0040] The compound represented by the above general formula (1) may be a single compound or a mixture of two or more compounds having different degrees of condensation or types of salts. Among these, X 1 This melamine is a phosphate compound represented by the above general formula (1), and X 1 It is preferable to include one or more of the phosphate compounds represented by the above general formula (1), which is ammonia. In addition, it is preferable that the phosphate compounds include pyrophosphate represented by the above general formula (1) where n1 is 2. When using the phosphate compounds as a mixture, it is preferable that the content ratio of pyrophosphate represented by the above general formula (1) where n1 is 2 is higher. By doing so, heat resistance can be stably improved.

[0041] Among the above general formula (2), Y 1 As a compound represented by, [R 21 R 22 N(CH2) m NR 23 R 24 Examples include ], piperazine, or diamines containing a piperazine ring. R 21 ~R 24It may be the same or different and represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 5 carbon atoms.

[0042] The above R 21 ~R 24 As a straight-chain or branched alkyl group having 1 to 5 carbon atoms represented by, for example, the above Z 1 and Z 2 Among the specific examples of alkyl groups represented by, there are those with 1 to 5 carbon atoms.

[0043] As diamines containing the above piperazine ring, for example, there are compounds in which one or more of the 2, 3, 5, and 6 positions of piperazine are substituted with an alkyl group (preferably 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 having 1 to 5 carbon atoms).

[0044] Y in the above general formula (2) 1 Examples of compounds represented by [the above] include, specifically, 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-propanediamine, 1,3-propanediamine, 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, 1,4-bis(3-aminopropyl)piperazine, etc.

[0045] The compound represented by the above general formula (2) may be a single compound or a mixture of two or more compounds having different degrees of condensation or types of salts. The above phosphate compound is Y 1It is preferable to include a phosphate compound represented by the general formula (2) above, which is piperazine. Additionally, it is preferable that the phosphate compound includes a pyrophosphate represented by the general formula (2) above, where n2 is 2. When using the phosphate compound as a mixture, it is preferable that the content ratio of the pyrophosphate with n2 being 2 be higher. By doing so, heat resistance can be stably improved.

[0046] As a method for manufacturing the above phosphate compound, for example, for a salt of phosphates and melamine such as melamine pyrophosphate, sodium pyrophosphate and melamine can be mixed in any ratio, then hydrochloric acid is added to react, and the mixture is neutralized with sodium hydroxide. Also, for example, for a salt of phosphates and piperazine, the phosphates and piperazine can be easily obtained as a water-insoluble precipitate by reacting them in any ratio in water or in an aqueous methanol solution. At this time, the composition of the phosphates in the raw material is not particularly limited. In addition, a phosphate compound in which n1 or n2 in the above general formula (1) or the above general formula (2) is 2 or more may be obtained by heating and condensing an orthophosphate in which n1 or n2 is 1.

[0047] Thus, the above-mentioned phosphate compounds are obtained. These may be used alone or in combination of two or more types. A flame retardant composition containing such phosphate compounds can impart excellent flame retardancy to resin materials.

[0048] In terms of flame retardancy, the flame retardant composition of the present invention preferably contains both the phosphate compound represented by the general formula (1) and the phosphate compound represented by the general formula (2).

[0049] In particular, X 1 This melamine is a phosphate compound represented by the above general formula (1), and Y 1It is preferable to use a phosphate compound represented by the above general formula (2), which is piperazine. In addition, it is also preferable to use a phosphate compound represented by the above general formula (1) where n1 is 2 and a phosphate compound represented by the above general formula (2) where n2 is 2.

[0050] In the case where 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 is preferably 20:80 to 60:40 in terms of flame retardancy, more preferably 25:75 to 55:45 in terms of mass ratio of the former and the latter, and even more preferably 30:70 to 50:50 in terms of mass ratio.

[0051] In addition, as mentioned above, the inventors' review revealed that the bulk density of the flame retardant composition affects the airborne properties of the dust.

[0052] Generally, it is believed that the lower the bulk density of a powder, the higher its dust dispersion. However, as a result of the inventors' examination, it was surprisingly found that the flame retardant composition of the present invention containing the specific phosphate compound above exhibits the opposite result. That is, it was found that when the loose bulk density of the flame retardant composition is high, the dispersion of the flame retardant composition increases.

[0053] Based on these findings, the inventors further examined the matter and found that by setting the ratio of the loose bulk density to the particle diameter distribution width of the flame retardant composition to a value greater than or less than a predetermined value, it is possible to achieve both the suppression of dust scattering and good powder fluidity of the flame retardant composition. In other words, simply suppressing the dust scattering of the powder may have a negative effect on powder fluidity, but the inventors' examination revealed that by appropriately setting the ratio of the loose bulk density to the particle diameter distribution width, the suppression of dust scattering and good powder fluidity can be achieved simultaneously.

[0054] Therefore, according to the flame retardant composition of the present invention, dust dispersion is suppressed, and the deterioration of the working environment caused by dust can be prevented. In addition, since the flame retardant composition of the present invention exhibits good powder fluidity, it is difficult to adversely affect productivity or dispersibility when mixed with resin materials.

[0055] The flame retardant composition of the present invention has a loose bulk density of d (g / cm³) of the flame retardant composition. 3 ), the cumulative 10% particle diameter in the volume-based particle diameter distribution is D 10 (㎛), cumulative 50% particle diameter D 50 When set to (㎛), d, D 10 and D 50 This satisfies the following equation (I).

[0056] 0.030≤d / (D 50 -D 10 )≤0.110 … (I)

[0057] Among the above equation (I), d / (D 50 -D 10 The lower limit of ) is 0.030 or higher, preferably 0.035 or higher, and more preferably 0.040 or higher. This allows for improved powder fluidity. Meanwhile, among the above formula (I), d / (D 50 -D 10 The upper limit of ) is 0.110 or less, preferably 0.107 or less, and more preferably 0.103 or less. This allows for suppressing excessive dust dispersion.

[0058] Here, the loose bulk density d is the packing density when the powder is allowed to fall naturally. The measurement of the loose bulk density is, for example, at a given 100 cm³ 3 A suitable amount of powder composition is dropped from the upper opening of a cylindrical container to loosely fill it, and the filled mass (g) is measured and the volume (cm²) is measured. 3 Perform a reading of ) and the volume (cm 3The mass (g) of the above powder composition can be calculated. The loose bulk density may be measured using a commercially available powder characteristic measuring device.

[0059] In addition, the cumulative 10% particle diameter D in the volume-based particle diameter distribution of the flame retardant composition 10 and cumulative 50% particle diameter D 50 For example, the size can be obtained by measuring the size using a laser diffraction and scattering particle size distribution measuring device for a flame retardant composition dispersed in methanol and ultrasonically treated.

[0060] In the flame retardant composition of the present invention, it is preferable that the value of the loose bulk density d satisfies the following formula (II).

[0061] 0.20≤d≤0.80 … (II)

[0062] In the above formula (II), the lower limit of d is 0.20 or higher, preferably 0.25 or higher, more preferably 0.30 or higher. This improves the fluidity of the powder. Meanwhile, the upper limit of d is 0.80 or lower, preferably 0.70 or lower, more preferably 0.60 or lower, even more preferably 0.55 or lower, and particularly preferably 0.50 or lower. This suppresses excessive dust scattering.

[0063] The above loose bulk density d, cumulative 10% particle diameter D 10 and cumulative 50% particle diameter D 50 This can be controlled, for example, by appropriately selecting preparation methods such as grinding or classification. Among these, for example, appropriately selecting grinding conditions such as the grinding method or grinding time, classification conditions such as the cutting of coarse particles, and blending conditions, etc., is the above-mentioned d and D 10 and D 50 It can be cited as an example of a factor for making it a desired numerical range. In addition, the aforementioned d, D 10and D 50 It can also be controlled by the presence or absence of surface treatment or by appropriately selecting a surface treatment agent. Examples of such surface treatment agents include the surface treatment agents, dust suppressants, and lubricants described later.

[0064] Examples of grinding means for the above grinding include a mortar and pestle, a ball mill, a rod mill, a tube mill, a conical mill, a vibrating ball mill, a high-swing ball mill, a roller mill, a pin mill, a hammer mill, an atrition mill, a jet mill, a jetmizer, a micronizer, a nanomizer, a mahjong mill, a micro-atomizer, a colloid mill, a premier colloid mill, a micron mill, a Charlotte colloid mill, a rotary cutter, a dry medium stirring mill, an impact type ultrafine grinder, a planetary mill, a bead mill, a micro bead mill, a grinding mill, a crushing roll, etc. These grinding means may be used individually or in combination of two or more types.

[0065] The above-mentioned classification means include, for example, dry classification such as sieve classification, tube classification, and centrifugal classification, or wet classification such as sedimentation classification. Grinding and classification may also be performed simultaneously using a grinder with a built-in classification function.

[0066] In the case where the flame retardant composition of the present invention is a mixture of multiple components, each component may be mixed after undergoing a preparation process such as grinding or classification, or the preparation process such as grinding or classification may be performed after each component is mixed.

[0067] The flame retardant composition of the present invention may contain an aid.

[0068] Examples of the above additives include flame retardants, drip prevention additives, and processing additives.

[0069] The above flame retardant may include metal oxides or polyhydric alcohol compounds. This can improve the flame retardancy of the resin.

[0070] Examples of the above 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 may be used individually or in combination of two or more types. This can improve the flame retardancy of the resin. Furthermore, it can suppress the occurrence of aggregation in the granular flame retardant composition. Among the above metal oxides, zinc oxide is preferred from the perspective of flame retardancy.

[0071] The above zinc oxide may or may not be surface-treated. Specifically, as the above zinc oxide, commercial products such as zinc oxide type 1 (manufactured by Mitsui Metal Industries, Inc.), partial film-type zinc oxide (manufactured by Mitsui Metal Industries, Inc.), Nanofine 50 (ultrafine zinc oxide with an average particle size of 0.02 μm: manufactured by Sakai Chemical Industries, Inc.), and Nanofine K (ultrafine zinc oxide coated with zinc silicate with an average particle size of 0.02 μm: manufactured by Sakai Chemical Industries, Inc.) may be used.

[0072] The above polyhydric alcohol compound is a compound in which a plurality of hydroxyl groups are bonded, and examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl)isocyanurate (THEIC), polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, etc. Among these polyhydric alcohol compounds, one or more selected from the group consisting of condensates of pentaerythritol and pentaerythritol, such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol, are preferred, condensates of dipentaerythritol and pentaerythritol are particularly preferred, and dipentaerythritol is most preferred. In addition, THEIC and sorbitol may also be preferably used. These may be used alone or in combination of two or more.

[0073] Examples of the above drip-prevention agents include layered silicates, fluorine-based drip-prevention agents, and silicone rubbers. By doing so, dripping during the combustion of the resin can be suppressed.

[0074] The above layered silicate is a layered silicate mineral, and may be either natural or synthetic, and is not particularly limited. Examples of the above layered silicates include smectite-based clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, as well as vermiculite, halloysite, swelling mica, and talc. These may be used individually or in combination of two or more types. Among the above layered silicates, saponite or talc is preferred from the perspective of preventing dripping, and talc is particularly preferred from the perspective of economic feasibility such as cost.

[0075] The above layered silicate may have cations between the layers. The cations may be metal ions, and some or all of them may be cations other than metal ions, such as organic cations, (quaternary) ammonium cations, phosphonium cations, etc.

[0076] Examples of the above metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, lithium ions, nickel ions, copper ions, zinc ions, etc.

[0077] Examples of the above organic cations or quaternary ammonium cations include lauryl trimethylammonium cation, stearyl trimethylammonium cation, trioctylmethylammonium cation, distearyl dimethylammonium cation, dihydrolyzed beef tallow dimethylammonium cation, distearyl dibenzylammonium cation, etc. These may be used individually or in combination of two or more types.

[0078] Specific examples of the above-mentioned fluorine-based anti-drip agent include, for instance, fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, or perfluoroalkanesulfonic acid alkali metal salt compounds such as sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, potassium perfluoro-tert-butanesulfonate, sodium perfluorooctanesulfonate, and calcium perfluoro-2-ethylhexanesulfonate, or perfluoroalkanesulfonic acid alkaline earth metal salts. Among these, polytetrafluoroethylene is preferred in terms of anti-drip properties. These may be used alone or in combination of two or more types.

[0079] The above processing aid may be appropriately selected from known processing aids, but may include an acrylic acid-based processing aid.

[0080] Examples of the above acrylic acid-based processing aids include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above alkyl methacrylates and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above alkyl methacrylates and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; copolymers of the above alkyl methacrylates and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These may be used individually or in combination of two or more types.

[0081] The above flame retardant composition may include a surface treatment agent.

[0082] Examples of the above surface treatment agents include silicone oil or silane coupling agents. By using the above silicone oil, it is possible to prevent aggregation of the powdered flame retardant composition, improve storage stability, and enhance dispersibility into synthetic resins. In addition, water resistance can be improved.

[0083] As for the above silicone oil, any known silicone oil having a polysiloxane backbone can be used without particular limitation. The above silicone oil may be a polymer having a straight-chain polysiloxane backbone, and all of the side chains of the polysiloxane may be methyl groups, some of the side chains may have phenyl groups, and some of the side chains may have hydrogen.

[0084] Examples of silicone oils include dimethyl silicone oil in which both the side chains and ends of the polysiloxane are methyl groups, methylphenyl silicone oil in which the side chains and ends of the polysiloxane are methyl groups and part of the side chain is a phenyl group, methylhydrogen silicone oil in which the side chains and ends of the polysiloxane are methyl groups and part of the side chain is hydrogen, and copolymers thereof. These silicone oils may have parts modified by epoxy modification, amino modification, carboxy modification, etc. These may be used individually or in combination of two or more types.

[0085] Among silicone oils, dimethyl silicone oil and methylhydrogen silicone oil are preferred, and methylhydrogen silicone oil is more preferred, in terms of preventing aggregation of powdered flame retardant compositions, improving storage stability, and improving dispersibility into synthetic resins.

[0086] As the above silane coupling agents, for example, as silane coupling agents having an alkenyl group, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, etc., as silane coupling agents having an acrylic group, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, etc., as silane coupling agents having a methacrylic group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxyoctyltrimethoxysilane, etc., and having an epoxy group As silane coupling agents, there are 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane, etc., and as silane coupling agents having an amino group, there are N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, There are hydrochloride salts of N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc., as silane coupling agents having an isocyanurate group, there is tris-(trimethoxysilylpropyl)isocyanurate, as silane coupling agents having a mercapto group, there are 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc., as silane coupling agents having a ureid group, there are 3-ureidpropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, etc., as silane coupling agents having a sulfide group, there is bis(triethoxysilylpropyl)tetrasulfide, and as silane coupling agents having a thioester group,There is 3-octanoylthio-1-propyltriethoxysilane, and as silane coupling agents having an isocyanate group, there are 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. These may be used alone or in combination of two or more types.

[0087] Among these silane coupling agents, a silane coupling agent having an epoxy group is preferred in terms of improving flame retardancy and handling properties, as well as preventing aggregation of the powder-type flame retardant composition and improving storage stability, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane are more preferred.

[0088] Methods for adding the above-mentioned surface treatment agent include, for example, a method of mixing the surface treatment agent with a granular flame retardant composition, or a method of adding and mixing the surface treatment agent by spray-drying it. Additionally, the above-mentioned surface treatment agent may be added to the flame retardant composition by surface-treating a portion of the components constituting the flame retardant composition.

[0089] The above flame retardant composition may include a dust suppressant.

[0090] Examples of the above dust suppressants include aliphatic dicarboxylic acid ether ester compounds or the aforementioned silane coupling agents.

[0091] The above aliphatic dicarboxylic acid ether ester compound may include a compound represented by the following general formula (3). This allows for the suppression of dust in the granular flame retardant composition. These may be used individually or in combination of two or more types.

[0092]

[0093] In the general formula (3), n3 represents an integer from 1 to 3, m3 represents an integer from 2 to 6, and R3 represents an alkyl group having 1 to 6 carbon atoms.

[0094] In the above general formula (3), R 3 The alkyl group having 1 to 6 carbon atoms represented by R can be a straight-chain alkyl group or a branched alkyl group, examples of which include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, and hexyl groups. 3 As such, butyl groups are preferred in terms of flame retardancy, and especially in terms of handling and storage stability.

[0095] In addition, in the above general formula (3), it is preferable that n3 be 2 in terms of flame retardancy, and especially in terms of handling and storage stability. In addition, in the above general formula (3), it is preferable that m3 be 4 in terms of flame retardancy, and especially in terms of handling and storage stability.

[0096] The flame retardant composition described above may include other components within a range that does not impair the effects of the present invention. As for other components, additives commonly used to modify thermoplastic resins may be used, such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization nucleating agents, clearing agents, plasticizers, lubricants, flame retardants other than the phosphate compounds according to the present invention, reinforcing agents, crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, anti-plate-out agents, fluorescent agents, antifungal agents, disinfectants, foaming agents, metal inerts, release agents, pigments, dyes, etc. These may be used individually or in combination of two or more types.

[0097] Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and other antioxidants.

[0098] As phenolic antioxidants, for example, 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)propionic acid amide], 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-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)isocyanurate, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 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], thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol 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,Examples include triethyleneglycolbis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc. These phenolic antioxidants may be used individually or in combination of two or more types.

[0099] As phosphite-based antioxidants, for example, trisnonylphenylphosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecylphosphite, octyldiphenylphosphite, didecylmonophenylphosphite, bis(tridecyl)pentaerythritoldiphosphite, bis(nonylphenyl)pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,4-dicumylphenyl)pentaerythritoldiphosphite, Tetrakis(tridecyl)isopropylidenediphenol diphosphite, Tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, Hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butanetriphosphite, Tetrakis(2,4-di-tert-butylphenyl)biphenylenediphosphonite, 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, Examples include 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphospherfin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropylene glycol, and 2,4,6-tri-tert-butylphenol phosphites. These phosphite-based antioxidants may be used individually or in combination of two or more types.

[0100] As thioether-based antioxidants, for example, 3,3'-thiodipropionic acid, alkyl(C12-14)thiopropionic acid, di(lauryl)-3,3'-thiodipropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3,3'-thiodipropionate, lauryl stearyl thiodipropionate, tetrakis[methylene-3-(dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propionate), 2,2'-thiodiethylenebis(3-aminobutenoate), 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), Examples include 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, and bis(methyl-4-[3-n-alkyl(C12 / C14)thiopropionyloxy]5-tert-butylphenyl)sulfide. These thioether-based antioxidants may be used individually or in combination of two or more types.

[0101] Other antioxidants include, for example, nitron compounds such as N-benzyl-α-phenylnitron, N-ethyl-α-methylnitron, N-octyl-α-heptylnitron, N-lauryl-α-undecylnitron, N-tetradecyl-α-tridecylnitron, N-hexadecyl-α-pentadecylnitron, N-octyl-α-heptadecylnitron, N-hexadecyl-α-heptadecylnitron, N-octadecyl-α-pentadecylnitron, N-heptadecyl-α-heptadecylnitron, N-octadecyl-α-heptadecylnitron, 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2-one, 3-(acyloxyphenyl)benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-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, There are benzofuran compounds such as 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran-2(3H)one. These other antioxidants may be used individually or in combination of two or more types.

[0102] As light stabilizers, for example, 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-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, Bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-Bis(2,2,6,6-tetramethyl-4-piperidylamino)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-piperidyl)amino)-s-triazine-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-piperidyl)amino)-s-triazine-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)decandioate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,3,4-butanetetracarboxylic acid, polymer with 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanale, 1,2,2,6,6-pentamethyl-4-piperidinyl ester, 1,3-bis(2,2,6,6-tetramethylpiperidin-4-yl)2,4-ditridecylbenzene-1,2,3,4-tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, Examples include poly[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]), and TINUVIN NOR371 manufactured by BASF. These light stabilizers may be used individually or in combination of two or more types.

[0103] As ultraviolet absorbers, for example, 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 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, etc.; Benzoates such as phenyl salicylate, resorcinol monobenzoate, 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 oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; There are triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-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 individually or in combination of two or more types.

[0104] As nucleating agents, for example, metal salts of carboxylic acids such as sodium benzoate, aluminum salt of 4-tert-butylbenzoate, sodium adipose, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, metal salts of phosphate esters such as sodium bis(4-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, bis(dimethylbenzylidene)sorbitol, Examples include polyhydric alcohol derivatives such as 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl)methylene)-nonitol, 1,3:2,4-bis(p-methylbenzylidene)sorbitol, and 1,3:2,4-bis-O-benzylidene-D-glucitol (dibenzylidene 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'-dicyclohexyl-naphthalenedicarboxamide, and 1,3,5-tri(dimethylisopropoyamino)benzene. These nucleating agents may be used individually or in combination of two or more types.

[0105] 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 acid and polyhydric alcohol, and polycondensates of polycarboxylic acid and polyhydric alcohol; polyetherester-based plasticizers such as polycondensates of dicarboxylic acid, polyhydric alcohol, and alkylene glycol, polycondensates of dicarboxylic acid, polyhydric alcohol, and arylene glycol, and polycondensates of polycarboxylic acid, polyhydric alcohol, and arylene glycol; aliphatic ester-based plasticizers such as adipic acid esters and succinic acid esters; and aromatic ester-based plasticizers such as phthalic acid esters, terephthalic acid esters, trimellitic acid esters, pyromellitic acid esters, and benzoic acid esters. These plasticizers may be used individually or in combination of two or more types.

[0106] Examples of lubricants include pure hydrocarbon lubricants such as commercial paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids; fatty acid amide lubricants such as fatty acid amides and bis fatty acid amides; ester lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters (ester waxes) of fatty acids; lubricants such as metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols, and partial esters of polyglycerols, silicone oils, and mineral oils. These lubricants may be used individually or in combination of two or more types.

[0107] As other flame retardants other than the phosphate compound according to the present invention, for example, triphenylphosphate, tricresylphosphate, trixyllenylphosphate, cresyl diphenylphosphate, cresyl-2,6-dicyllenylphosphate, resorcinolbis(diphenylphosphate), (1-methylethylidene)-4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, aromatic phosphate esters such as "Adecastav FP-500", "Adecastav FP-600", "Adecastav FP-800", and "Adecastav FP-900L" manufactured by ADEKA Co., Ltd., phosphonic acid esters such as divinyl phenylphosphonic acid, diallyl phenylphosphonic acid, and phenyl(1-butenyl) phenyl diphenylphosphinate, Phosphic acid esters such as methyl diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, dialkylphosphinates such as aluminum diethylphosphine and zinc diethylphosphine, phosphagen compounds such as bis(2-allylphenoxy)phosphagen and dicresylphosphagen, inorganic phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromozyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, There are brominated flame retardants such as bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol type A dimethacrylate, pentabromobenzyl acrylate, and brominated styrene. These other flame retardants may be used individually or in combination of two or more types.

[0108] 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 ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate ester salts, higher alcohol ethylene oxide adduct sulfate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts; nonionic antistatic agents such as polyhydric alcohol fatty acid esters, polyglycol phosphate esters, and polyoxyethylenealkylallyl ethers; amphoteric alkyl betaines such as alkyldimethylaminoacetic acid betaine; and amphoteric antistatic agents such as imidazoline-type amphoteric activators. These antistatic agents may be used individually or in combination of two or more types.

[0109] Examples of fillers include 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, silica, alumina, potassium titanate whiskers, wallastenite, fibrous magnesium oxysulfate, montmorillonite, etc., and the particle diameter (in the case of fibrous materials, fiber diameter, fiber length, and aspect ratio) can be appropriately selected and used. These fillers may be used as a single type or in combination of two or more types. In addition, surface-treated fillers may be used as needed.

[0110] As a pigment, for example, 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, 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 individually or in combination of two or more types.

[0111] Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthen dyes, alizarin dyes, acridin dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc. These dyes may be used individually or in combination of two or more types.

[0112] In addition, one or more of the aforementioned preparations, surface treatment agents, dust suppressants, and other components may be incorporated into the flame retardant composition, but may also be incorporated into a flame retardant resin composition comprising the flame retardant composition and a thermoplastic resin.

[0113] The flame retardant composition of the present invention can be obtained by mixing one or more of the phosphate compounds represented by general formula (1) or general formula (2) and, if necessary, other optional components, on the condition that the above formula (I) is satisfied. Various types of mixers may be used for mixing. Heating may be performed during mixing. Examples of mixers that can be used are not particularly limited, but include tumbler mixers, Henkel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, etc.

[0114] In addition, if the flame retardant composition obtained by mixing does not satisfy the above formula (I), it can be adjusted to satisfy the above formula (I) by adding a surface treatment agent or a dust suppressant, or by grinding in a grinder.

[0115] Flame-retardant resin composition

[0116] The flame-retardant resin composition of the present invention contains the aforementioned flame-retardant composition and a thermoplastic resin.

[0117] The content of the flame retardant composition above can be typically 10 to 400 parts by mass per 100 parts by mass of the thermoplastic resin, preferably 15 to 200 parts by mass, and more preferably within the range of 20 to 70 parts by mass. By doing so, the flame retardancy of the thermoplastic resin can be sufficiently improved.

[0118] Examples of the above thermoplastic resins include synthetic resins such as polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins. These may be used individually or in combination of two or more types.

[0119] In addition, examples of the above thermoplastic resins include, for instance, petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose-based resin, polyimide resin, polysulfone, liquid crystal polymer, and blends thereof.

[0120] In addition, the above thermoplastic resin may 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-based elastomer, styrene-based elastomer, polyester-based elastomer, nitrile-based elastomer, nylon-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, or polyurethane-based elastomer, and these may be used in combination.

[0121] Specific examples of the above thermoplastic resin are not particularly limited, but include, for example, polyolefin-based resins such as polypropylene, high-density polyethylene, low-density polyethylene, straight-chain low-density polyethylene, polybutene-1, poly3-methylpentene, poly4-methylpentene, ethylene / propylene block or random copolymer, etc.; thermoplastic straight-chain polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, etc.; polysulfide-based resins such as polyphenylene sulfide; polylactic acid-based resins such as polycaprolactone; straight-chain polyamide-based resins such as polyhexamethylene adipamide; crystalline polystyrene-based resins such as syndiotactic polystyrene, etc.

[0122] These thermoplastic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in the solvent, degree of stereoregularity, presence or absence of catalyst residue, type or blending ratio of raw monomers, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.).

[0123] Among these thermoplastic resins, one or more selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof are preferred in that they can impart excellent flame retardancy, polyolefin resins are more preferred, polypropylene, high-density polyethylene, low-density polyethylene, and straight-chain low-density polyethylene are even more preferred, and it is also preferred to use these together with a thermoplastic elastomer.

[0124] The flame-retardant resin composition may, in addition to the flame-retardant composition, include, if necessary, one or more additives selected from the aforementioned preparations, surface treatment agents, dust suppressants, and other components. These may be used individually or in combination of two or more types.

[0125] The content of the additive (excluding fillers and flame retardants other than phosphate compounds according to the present invention) in the above flame-retardant resin composition is, for example, 0.001 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, preferably 0.005 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass. By setting the numerical range to this, an improvement in the effect of the additive is obtained.

[0126] When a filler is incorporated into the flame-retardant resin composition, the content thereof is, for example, 1 to 100 parts by mass per 100 parts by mass of thermoplastic resin, preferably 3 to 80 parts by mass, and more preferably 5 to 50 parts by mass.

[0127] When a flame retardant other than the phosphate compound according to the present invention is incorporated into the flame-retardant resin composition, the content thereof is, for example, 1 to 200 parts by mass per 100 parts by mass of the thermoplastic resin, preferably 3 to 150 parts by mass, and more preferably 5 to 80 parts by mass.

[0128] In the above flame-retardant resin composition, when a polyolefin-based resin or an olefin-based elastomer is used as the thermoplastic resin, it is preferable that the flame-retardant resin composition contains a known neutralizing agent within a range that does not impair the effects of the present invention in order to neutralize catalyst residues in the resin. Examples of neutralizing agents include metal salts of fatty acids such as calcium stearate, lithium stearate, sodium stearate, and magnesium stearate; fatty acid amide compounds such as ethylenebis(stearic acid amide), ethylenebis(12-hydroxystearic acid amide), and stearic acid amide; or inorganic compounds such as hydrotalcite. One of these neutralizing agents may be used alone, or two or more may be used in combination. The amount of these neutralizing agents used is preferably 0.001 to 3 parts by mass per 100 parts by mass of the thermoplastic resin, and more preferably 0.01 to 1 part by mass.

[0129] Next, a method for manufacturing the flame-retardant resin composition is described.

[0130] The above flame-retardant resin composition can be obtained by mixing the aforementioned flame-retardant composition with a thermoplastic resin. If necessary, the above additive may be mixed. The additive may be mixed into the flame-retardant composition or into the mixture of the flame-retardant composition and the thermoplastic resin.

[0131] As for the mixing method, commonly used known methods may be applied as is. For example, methods include mixing the flame retardant composition, the thermoplastic resin, and additives as needed using a conventional blender or mixer, melt-kneading using an extruder, or mixing with a solvent and solution-casting.

[0132] The flame-retardant resin composition above can be used in various forms, for example, any one of pellets, granules, or powders. From the perspective of handling ease, the pellet form is preferred.

[0133] Plastic body

[0134] The molded article of the present invention is formed using the flame-retardant resin composition. A molded article can be manufactured by molding using the flame-retardant resin composition.

[0135] The above molding method is not particularly limited and examples include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendering, slush molding, dip molding, foam molding, and addition manufacturing methods. Among these, injection molding, extrusion molding, and blow molding are preferred.

[0136] Thus, molded bodies of various shapes, such as resin plates, sheets, films, and molded products, can be manufactured.

[0137] A molded article made using the above flame-retardant resin composition can be used for various purposes, such as electrical and electronic components, mechanical parts, optical instruments, building materials, automotive parts, and daily necessities. Among these, it can be preferably used for electrical and electronic components and building materials from the perspective of flame retardancy.

[0138] The above flame-retardant resin composition and the molded article thereof can be used in a wide range of industrial fields, such as, for example, electrical, electronic, and telecommunications, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing, musical instruments, etc. Specifically, the flame-retardant resin composition and the molded body thereof of the present invention can be used in office and OA equipment such as printers, PCs, word processors, keyboards, PDAs (small information terminal devices), telephones, photocopiers, fax machines, ECRs (electronic cash registers), electronic calculators, electronic notebooks, cards, holders, stationery, etc., home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, kotatsu, etc., AV equipment such as TVs, VTRs, video cameras, radio cassettes, tape recorders, minidiscs, CD players, speakers, liquid crystal displays, etc., and electrical and electronic components and communication devices such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, wires, cables, transformers, deflection yokes, distribution boards, and clocks.

[0139] The above flame-retardant resin composition and its molded articles are, for example, materials for automobiles, vehicles, ships, aircraft, buildings, houses, etc., construction materials or civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiberboard, carpets, door visors, seats, wheel covers, mattress covers, airbags, insulation materials, straps, strap belts, wire sheathing materials, electrical insulation materials, paints, coating materials, wallpapering materials, flooring materials, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, decking materials, wall materials, column materials, footrests, fence materials, frames and moldings, window and door shapes, boards, panels, terraces, balconies, soundproofing panels, insulation panels, window materials, etc., household goods such as construction materials or civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiberboard, carpets, doormats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, ski plates, rackets, tents, musical instruments, etc., It can be used in various fields such as sports equipment.

[0140] Although embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above may be adopted. Furthermore, the present invention is not limited to the aforementioned embodiments, and modifications and improvements within the scope of achieving the objectives of the present invention are included in the present invention.

[0141] Examples

[0142] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way by the description of these examples.

[0143] <Manufacture of Melamine Salt>

[0144] Melamine orthophosphate was heated and condensed in a solid state at 220°C for 6 hours to produce a melamine salt with melamine pyrophosphate as the main component. The melamine salt was used as is without purification. The purity of melamine pyrophosphate in the melamine salt was 98.5%.

[0145] <Preparation of Piperazine Salt>

[0146] Piperazine diphosphate was heated and condensed in a solid state at 250°C for 1 hour to produce a piperazine salt with piperazine pyrophosphate as the main component. The piperazine salt was used as is without purification. The purity of piperazine pyrophosphate in the piperazine salt was 99.0%.

[0147] The purity of the above melamine salt and piperazine salt was measured using an ion chromatograph measuring device ICS-2100 (manufactured by Thermo Fisher Scientific Co., Ltd.), a Dionex IonPac AS-19 column (manufactured by Thermo Fisher Scientific Co., Ltd.), and an electrical conductivity detector.

[0148] <Preparation of Composition A1>

[0149] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 0.3 parts by mass of methylhydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.3 parts by mass of dimethyl silicone oil (KF-96, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was mixed using a food mixer to obtain composition A1.

[0150] <Preparation of Composition A2>

[0151] 35 parts by mass of the above melamine salt, 5 parts by mass of polyphosphate melamine (PMP100, manufactured by Nissan Chemical Co., Ltd.), 60 parts by mass of the above piperazine salt, and 5 parts by mass of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 0.3 parts by mass of methylhydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.3 parts by mass of butyl stearate were mixed using a food mixer to obtain composition A2.

[0152] <Preparation of Composition A3>

[0153] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 0.3 parts by mass of methylhydrogen silicone oil (KF-9901, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were mixed using a food mixer and heated to 150°C in a heating oven. After 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 mixer to obtain composition A3.

[0154] <Preparation of Composition A4>

[0155] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila Ace S530, manufactured by JNC Corporation) was mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.2 parts by mass of bis[2-(2-butoxyethoxy)ethyl] adipic acid were mixed using a food mixer to obtain composition A4.

[0156] <Preparation of Composition A5>

[0157] 40 parts by mass of the above melamine salt and 60 parts by mass of the above piperazine salt were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation, Inc.) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding rate 100 g / h, and 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.2 parts by mass of bis[2-(2-butoxyethoxy)ethyl adipic acid were mixed using a food mixer to obtain composition A5.

[0158] <Preparation of Composition A6>

[0159] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Enterprise Co., Ltd.) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.2 parts by mass of polyethylene glycol dioctylate (300) were mixed using a food mixer to obtain composition A6.

[0160] <Preparation of Composition A7>

[0161] 35 parts by mass of the above melamine salt, 5 parts by mass of polyphosphate melamine (PMP100, manufactured by Nissan Chemical Co., Ltd.), and 60 parts by mass of the above piperazine salt were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding speed 100 g / h, and 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila Ace S530, manufactured by JNC Co., Ltd.) was mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.2 parts by mass of dioctyl polyethylene glycol (300) was mixed using a food mixer to obtain composition A7.

[0162] <Preparation of Composition A8>

[0163] Composition A8 was obtained by mixing and grinding (for 2 minutes) 70 parts by mass of polyammonium phosphate (Exolit AP422, manufactured by Clariant), 20 parts by mass of poly-[2,4-(piperazine-1,4-yl)-6-(morpholine-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 using a food mixer.

[0164] <Preparation of Composition A9>

[0165] Composition A9 was obtained by mixing and grinding (for 2 minutes) 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-(piperazine-1,4-yl)-6-(morpholine-4-yl)-1,3,5-triazine] and 0.2 parts by mass of stearic acid using a food mixer.

[0166] <Preparation of Composition A10>

[0167] 60 parts by mass of the above piperazine salt and 40 parts by mass of polyphosphate melamine (PMP100, manufactured by Nissan Chemical Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Co., Ltd.) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding rate 100 g / h, and 0.2 parts by mass of stearic acid were mixed using a food mixer to obtain composition A10.

[0168] <Preparation of Composition A11>

[0169] 70 parts by mass of ammonium polyphosphate (Exolit AP422, manufactured by Clariant Co., Ltd.) and 30 parts by mass of melamine cyanurate (MC-4000, manufactured by Nissan Chemical Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Co., Ltd.) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding rate 200 g / h, and 0.2 parts by mass of stearic acid were mixed using a food mixer to obtain composition A11.

[0170] <Preparation of Composition B1>

[0171] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding rate 100 g / h, and 0.3 parts by mass of methylhydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were mixed using a food mixer and heated to 150°C in a heating oven to obtain composition B1.

[0172] <Preparation of Composition B2>

[0173] 35 parts by mass of the above melamine salt, 5 parts by mass of polyphosphate melamine (PMP100, manufactured by Nissan Chemical Co., Ltd.), 60 parts by mass of the above piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding speed 100 g / h, mixed with 0.3 parts by mass of methylhydrogen silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) using a food mixer, and heated to 150°C in a heating oven to obtain composition B2.

[0174] <Preparation of Composition B3>

[0175] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 0.4 parts by mass of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding speed 100 g / h, and 0.3 parts by mass of methylhydrogen silicone oil (KF-9901, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were mixed using a food mixer and heated to 150°C in a heating oven to obtain composition B3.

[0176] <Preparation of Composition B4>

[0177] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding rate 100 g / h, and 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila Ace S530, manufactured by JNC Corporation) was mixed using a food mixer and heated to 150°C in a heating oven to obtain composition B4.

[0178] <Preparation of Composition B5>

[0179] 40 parts by mass of the above melamine salt and 60 parts by mass of the above piperazine salt were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation, Inc.) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding rate 100 g / h, mixed with 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry, Inc.) using a food mixer, and heated to 150°C in a heating oven to obtain composition B5.

[0180] <Preparation of Composition B6>

[0181] 40 parts by mass of the above melamine salt, 60 parts by mass of the above piperazine salt, and 5 parts by mass of one type of zinc oxide (manufactured by Mitsui Metal Mining Co., Ltd.) were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding rate 100 g / h, and 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was mixed using a food mixer and heated to 150°C in a heating oven to obtain composition B6.

[0182] <Preparation of Composition B7>

[0183] 35 parts by mass of the above melamine salt, 5 parts by mass of polyphosphate melamine (PMP100, manufactured by Nissan Chemical Co., Ltd.), and 60 parts by mass of the above piperazine salt were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Co., Ltd.) under conditions of P nozzle pressure 0.5 to 0.7 MPa, G nozzle pressure 0.5 to 0.65 MPa, and sample feeding rate 100 g / h, mixed with 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila Ace S530, manufactured by JNC Co., Ltd.) using a food mixer, and heated to 150°C in a heating oven to obtain composition B7.

[0184] <Preparation of Composition B8>

[0185] 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 mixer to obtain composition B8.

[0186] <Preparation of Composition B9>

[0187] 40 parts by mass of the above melamine salt and 60 parts by mass of the above piperazine salt were ground for 2 minutes using a food mixer, and 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silaace S530, manufactured by JNC Co., Ltd.) was mixed using a food mixer and heated to 150°C in a heating oven. After cooling to room temperature, 0.3 parts by mass of adipic acid bis[2-(2-butoxyethoxy)ethyl] were mixed using a food mixer to obtain composition B9.

[0188] <Preparation of Composition B10>

[0189] 100 parts by mass of composition B1 were ground using a compact jet mill grinder (Cojet System α-mkIII, manufactured by Seishin Corporation, Inc.) under conditions of P nozzle pressure 0.5–0.7 MPa, G nozzle pressure 0.5–0.65 MPa, and sample feeding rate 50 g / h, mixed with 1 part by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Sila Ace S530, manufactured by JNC Corporation) using a food mixer, and heated to 150°C in a heating oven to obtain composition B10.

[0190] For the flame retardant composition obtained above, measurements were performed on the following measurement items. The measurement results and the values ​​calculated based on Equation (I) from these measurement results are shown in Tables 1 to 3.

[0191] Measurement of Loose Volume Density

[0192] Using a powder property evaluation device (Multitester MT-02, manufactured by Seishin Corporation), diameter 5 cm, volume 100 cm 3 Using a cylindrical container, the loose bulk density of the obtained flame retardant composition was measured.

[0193] The sample was quietly filled into the container until it was heaping, the excess sample above the surface of the container was trimmed off, and the weight of the coarsely filled sample was measured. At this time, the loose bulk density (g / cm³) 3 ) is the weight of the sample pre-filled in the container (g) ÷ 100 (cm³ 3 Calculated from ).

[0194] Measurement of Particle Diameter Distribution

[0195] Cumulative 10% particle diameter D 10 and cumulative 50% particle diameter D 50 The obtained flame retardant composition was added to methanol and mixed, and the solution was dispersed by ultrasound while measuring the particle size distribution using a laser diffraction and scattering type particle size measuring device (Microtrack MT3000II, manufactured by Microtrack Bel Co., Ltd.) under wet conditions.

[0196] In addition, the obtained flame retardant composition was evaluated for the following evaluation items. The evaluation results are shown in Tables 1 to 3.

[0197] <Evaluation of Dust Dispersibility>

[0198] As shown in FIG. 1, a transparent acrylic tube (10) (outer diameter: 110 mm, inner diameter: 98 mm, length: 500 mm) with only one end open was set up with the top opening, and the three sides were surrounded by black acrylic plates (11). 10 g of the flame retardant composition obtained above was weighed and dropped free-falling from the top opening of the tube (10), and the appearance of the scattered dust was captured with a video camera. From the captured video, the state 5 seconds after the powder contacted the bottom surface was extracted as an image, and the luminance defined in the HLS color space of the part (12) about 150 mm from the bottom of the tube was extracted from the image. In addition, the brightness when a standard white plate (X 94.62, Y 99.79, Z 106.92 (SCI method)) is installed in part (12) and the brightness before dropping the flame retardant composition were extracted equally. The degree of dust scattering was calculated by the following formula (III).

[0199]

[0200] In Equation (III), (Sample) represents the brightness of the part (12) when the flame retardant composition is dropped, (White) represents the brightness of the part (12) when a standard white plate is installed in the part (12), and (Black) represents the brightness of the part (12) before the flame retardant composition is dropped.

[0201] The smaller the value calculated by Equation (III), the lower the dust dispersion of the flame retardant composition. And if this value is 30 or higher, it is a level where dust causes adverse effects to the working environment when supplying the flame retardant composition to a mixer or processing machine. This value is shown in Tables 1 to 3 as an evaluation value of dust dispersion.

[0202] Evaluation of Angle of Repose

[0203] The flame retardant composition was poured and deposited onto a disc using a funnel, and the angle at which it remained stable without collapsing was measured as the angle of repose (°). A lower value indicates better fluidity of the flame retardant composition.

[0204] Also, if the angle of repose is 60° or more, clogging is likely to occur in the hopper or feeder when processing the flame retardant composition, which is undesirable.

[0205] <Preparation of Test Specimens for Flame Retardancy Evaluation>

[0206] A flame-retardant resin composition was obtained by adding 54 parts by mass of the flame retardant composition (A1~A11, B1~B10) to a polypropylene resin composition obtained by blending 100 parts by mass of polypropylene (melt flow rate (in accordance with JIS K7210, load 2.16 kg, temperature 230℃) = 14 g / 10 min), 0.1 parts by mass of calcium stearate (neutralizing agent), 0.1 parts by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicate methyl]methane (phenolic antioxidant), and 0.1 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite (phosphorus-based antioxidant). The obtained flame-retardant resin composition was melt-kneaded using a twin-screw extruder (TEX28V, manufactured by Nippon Steel Works Co., Ltd.) under conditions of a cylinder temperature of 200–230°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 Corp.) under conditions of a cylinder temperature of 220°C and a mold temperature of 40°C to obtain a test specimen of 127 mm × 12.7 mm × 1.6 mm.

[0207] Flame Retardancy Evaluation

[0208] Using the obtained test specimens, a flame retardancy evaluation test was performed according to the UL-94V standard.

[0209] A test specimen measuring 127 mm in length, 12.7 mm in width, and 1.6 mm in thickness was held vertically, and a burner flame was applied to the bottom for 10 seconds. After removing the flame, the time it took for the fire ignited on the test specimen to disappear was measured. Next, as the fire disappeared, a second application of flame was initiated for 10 seconds, and the time it took for the ignited fire to disappear was measured in the same manner as the first application. Additionally, whether the cotton surface beneath the test specimen ignited due to falling embers was evaluated simultaneously.

[0210] Combustion ranks were assigned according to the UL-94V standard based on the first and second combustion times, the presence or absence of surface ignition, etc. The highest combustion rank is V-0, and flame retardancy decreases as it goes down to V-1 and V-2. However, those that do not fall into any of the ranks from V-0 to V-2 were classified as NR.

[0211] [Table 1]

[0212]

[0213] [Table 2]

[0214]

[0215] [Table 3]

[0216]

[0217] Regarding flame retardancy, it was good in all Examples 1 to 11 and Comparative Examples 1 to 10.

[0218] Meanwhile, regarding the evaluation of dust dispersion, Examples 1 to 11 were satisfactory, but Comparative Examples 1 to 7 showed values ​​higher than 30, indicating that they were at a level that adversely affects the working environment.

[0219] In addition, regarding the evaluation of the angle of repose, Examples 1 to 11 were good, but Comparative Examples 8 to 10 showed values ​​higher than 60° and were found to be inferior in terms of powder fluidity.

[0220] From the above, it can be seen that the flame retardant composition of the present invention has good powder fluidity, low dust scattering, and also exhibits good flame retardant performance. Explanation of the symbols

[0221] 10: Tong 11: Acrylic plate 12: The part approximately 150mm from the bottom of the container

Claims

Claim 1 A flame retardant composition containing one or more phosphate compounds represented by the following general formula (1) or the following general formula (2), wherein the loose bulk density of the flame retardant composition is d (g / cm²). 3 ), the cumulative 10% particle diameter in the volume-based particle diameter distribution of the flame retardant composition is D 10 (㎛), cumulative 50% particle diameter D 50 When set to (㎛), d, D 10 and D 50 This flame retardant composition satisfies the following formula (I), wherein the flame retardant composition further comprises one or more of zinc oxide and a silane coupling agent: 0.030≤d / (D 50 -D 10 )≤0.110 … (I) In the above general formula (1), n1 represents a number from 1 to 100, and X 1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p is 0 <p≤n1+2를 만족시키는 수를 나타내고, Among the above general formula (1-A), Z 1 and Z 2 is, each independently, -NR 11 R 12 It represents any one group selected from the group consisting of a hydroxyl group, a mercapto group, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group, and R 11 and R 12 Each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a methylol group, and In the above general formula (2), n2 represents a number from 1 to 100, and Y 1 [R 21 R 22 N(CH2) m NR 23 R 24 ], piperazine, or, representing a diamine containing a piperazine ring, and R 21 , R 22 , R 23 and R 24 Each independently represents a straight-chain or branched alkyl group having 1 to 5 hydrogen atoms or carbon atoms, m is an integer from 1 to 10, and q is 0 <q≤n2+2를 만족시키는 수를 나타냄. Claim 2 In claim 1, the flame retardant composition, wherein d satisfies the following formula (II): 0.20 ≤ d ≤ 0.80 … (II) Claim 3 In paragraph 1 or 2, X 1 A flame retardant composition containing the phosphate compound represented by the general formula (1) above, which is melamine. Claim 4 In paragraph 1 or 2, Y 1 A flame retardant composition containing the phosphate compound represented by the general formula (2) above, which is piperazine. Claim 5 In paragraph 1 or 2, X 1 A flame retardant composition containing the phosphate compound represented by the above general formula (1), which is ammonia. Claim 6 In paragraph 1 or 2, X 1 This melamine is the phosphate compound represented by the above general formula (1) and Y 1 A flame retardant composition containing the phosphate compound represented by the general formula (2) above, which is piperazine. Claim 7 A flame retardant composition according to claim 1 or 2, comprising the phosphate compound represented by the general formula (1) where n1 is 2 and the phosphate compound represented by the general formula (2) where n2 is 2. Claim 8 A flame-retardant resin composition containing a thermoplastic resin and a flame-retardant composition as described in claim 1 or 2. Claim 9 In claim 8, the flame-retardant resin composition wherein the thermoplastic resin contains a polyolefin-based resin. Claim 10 A molded article made using the flame-retardant resin composition described in paragraph 9.

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